Organic electroluminescent materials and devices

ABSTRACT

A compound comprising a ligand LA of Formula I,is disclosed. In Formula I, each of Z1, Z2, Z3, Z4, Z5, and Z6 is C or N; K is selected from a direct bond, O, and S; if K is O or S, then Z6 is C; ligand LA is coordinated to a metal by the dash lines; M is coordinated to at least one other ligand; L1 is an organic linker; if M is selected from Ru, Os, or Ir, then K is O or S; if M is selected from Pt, Pd, Cu, Ag, or Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur; when M is selected from Pt, Pd, Cu, Ag, or Au, and K is O or S, then L1 is selected from —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.63/024,566, filed May 14, 2020, and U.S. Provisional Application No.63/155,914, filed Mar. 3, 2021, the entire contents of which areincorporated by reference herein.

FIELD

The present disclosure generally relates to organometallic compounds andformulations and their various uses including as emitters in devicessuch as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for various reasons. Many of the materials usedto make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting diodes/devices (OLEDs), organic phototransistors, organicphotovoltaic cells, and organic photodetectors. For OLEDs, the organicmaterials may have performance advantages over conventional materials.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Alternatively, the OLED can be designed to emit white light. Inconventional liquid crystal displays emission from a white backlight isfiltered using absorption filters to produce red, green and blueemission. The same technique can also be used with OLEDs. The white OLEDcan be either a single emissive layer (EML) device or a stack structure.Color may be measured using CIE coordinates, which are well known to theart.

SUMMARY

In one aspect, the present disclosure provides a compound comprising aligand L_(A) of Formula I,

In Formula I:

each of Z¹, Z², Z³, Z⁴, Z⁵, and Z⁶ is independently C or N;

K is selected from the group consisting of a direct bond, O, and S;

when K is O or S, then Z⁶ is C;

each of ring A1 and ring A2 is independently a 5-membered or 6-memberedcarbocyclic or heterocyclic rings or a multicyclic fused-ring systemcomprising more than one 5-membered or 6-membered carbocyclic orheterocyclic ring;

each of R^(A) and R^(B) is independently mono, up to a maximum allowedsubstitutions, or no substitution;

ligand L_(A) is coordinated to a metal M by the two indicated dashlines;

M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag,and Au;

M is coordinated to at least one other ligand;

L_(A) can be joined with other ligands to form a tridentate,tetradentate, pentadentate, or hexadentate ligand;

L¹ is an organic linker;

when M is selected from the group consisting of Ru, Os, and Ir, then Kis O or S;

when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au,and K is a direct bond, then M forms at least one bond to oxygen orsulfur;

when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au,and K is O or S, then L¹ is selected from the group consisting of—CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—,—CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR₂—, —C(═N—)—, and —C(═CR—)—;

each R^(A), R^(B), R, R′, R″ is independently a hydrogen or asubstituent selected from the group consisting of deuterium, halogen,alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and

any two adjacent R^(A), R^(B), R, R′ and R″ can be joined or fusedtogether to form a ring.

In another aspect, the present disclosure provides a formulation of thecompound of the present disclosure.

In yet another aspect, the present disclosure provides an OLED having anorganic layer comprising the compound of the present disclosure.

In yet another aspect, the present disclosure provides a consumerproduct comprising an OLED with an organic layer comprising the compoundof the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

FIG. 3 shows photolumnescent spectra of inventive complexIr[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂.

FIG. 4 shows photolumnescent spectra of inventive complexIr[L_(A)1-(33)(2)(1)(1)][L_(B28)]₂.

FIG. 5 shows photolumnescent spectra of inventive complexIr[L_(A)1-(33)(2)(1)(1)][L_(B540)]₂.

DETAILED DESCRIPTION A. Terminology

Unless otherwise specified, the below terms used herein are defined asfollows:

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processable” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

The terms “halo,” “halogen,” and “halide” are used interchangeably andrefer to fluorine, chlorine, bromine, and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)—R_(s)).

The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R_(s) or—C(O)—O—R_(s)) radical.

The term “ether” refers to an —OR_(s) radical.

The terms “sulfanyl” or “thio-ether” are used interchangeably and referto a —SR radical.

The term “sulfinyl” refers to a —S(O)—R_(s) radical.

The term “sulfonyl” refers to a —SO₂—R_(s) radical.

The term “phosphino” refers to a —P(R_(s))₃ radical, wherein each R_(s)can be same or different.

The term “silyl” refers to a —Si(R_(s))₃ radical, wherein each R_(s) canbe same or different.

The term “boryl” refers to a —B(R_(s))₂ radical or its Lewis adduct—B(R_(s))₃ radical, wherein R_(s) can be same or different.

In each of the above, R_(s) can be hydrogen or a substituent selectedfrom the group consisting of deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl,alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, andcombination thereof. Preferred R_(s) is selected from the groupconsisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinationthereof.

The term “alkyl” refers to and includes both straight and branched chainalkyl radicals. Preferred alkyl groups are those containing from one tofifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl,butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, and the like. Additionally, the alkyl group may beoptionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, andspiro alkyl radicals. Preferred cycloalkyl groups are those containing 3to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl,cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl,adamantyl, and the like. Additionally, the cycloalkyl group may beoptionally substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or acycloalkyl radical, respectively, having at least one carbon atomreplaced by a heteroatom. Optionally the at least one heteroatom isselected from O, S, N, P, B, Si and Se, preferably, O, S or N.Additionally, the heteroalkyl or heterocycloalkyl group may beoptionally substituted.

The term “alkenyl” refers to and includes both straight and branchedchain alkene radicals. Alkenyl groups are essentially alkyl groups thatinclude at least one carbon-carbon double bond in the alkyl chain.Cycloalkenyl groups are essentially cycloalkyl groups that include atleast one carbon-carbon double bond in the cycloalkyl ring. The term“heteroalkenyl” as used herein refers to an alkenyl radical having atleast one carbon atom replaced by a heteroatom. Optionally the at leastone heteroatom is selected from O, S, N, P, B, Si, and Se, preferably,O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups arethose containing two to fifteen carbon atoms. Additionally, the alkenyl,cycloalkenyl, or heteroalkenyl group may be optionally substituted.

The term “alkynyl” refers to and includes both straight and branchedchain alkyne radicals. Alkynyl groups are essentially alkyl groups thatinclude at least one carbon-carbon triple bond in the alkyl chain.Preferred alkynyl groups are those containing two to fifteen carbonatoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer toan alkyl group that is substituted with an aryl group. Additionally, thearalkyl group may be optionally substituted.

The term “heterocyclic group” refers to and includes aromatic andnon-aromatic cyclic radicals containing at least one heteroatom.Optionally the at least one heteroatom is selected from O, S, N, P, B,Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals maybe used interchangeably with heteroaryl. Preferred hetero-non-aromaticcyclic groups are those containing 3 to 7 ring atoms which includes atleast one hetero atom, and includes cyclic amines such as morpholino,piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers,such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and thelike. Additionally, the heterocyclic group may be optionallysubstituted.

The term “aryl” refers to and includes both single-ring aromatichydrocarbyl groups and polycyclic aromatic ring systems. The polycyclicrings may have two or more rings in which two carbons are common to twoadjoining rings (the rings are “fused”) wherein at least one of therings is an aromatic hydrocarbyl group, e.g., the other rings can becycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls.Preferred aryl groups are those containing six to thirty carbon atoms,preferably six to twenty carbon atoms, more preferably six to twelvecarbon atoms. Especially preferred is an aryl group having six carbons,ten carbons or twelve carbons. Suitable aryl groups include phenyl,biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene,anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene,perylene, and azulene, preferably phenyl, biphenyl, triphenyl,triphenylene, fluorene, and naphthalene. Additionally, the aryl groupmay be optionally substituted.

The term “heteroaryl” refers to and includes both single-ring aromaticgroups and polycyclic aromatic ring systems that include at least oneheteroatom. The heteroatoms include, but are not limited to O, S, N, P,B, Si, and Se. In many instances, O, S, or N are the preferredheteroatoms. Hetero-single ring aromatic systems are preferably singlerings with 5 or 6 ring atoms, and the ring can have from one to sixheteroatoms. The hetero-polycyclic ring systems can have two or morerings in which two atoms are common to two adjoining rings (the ringsare “fused”) wherein at least one of the rings is a heteroaryl, e.g.,the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles,and/or heteroaryls. The hetero-polycyclic aromatic ring systems can havefrom one to six heteroatoms per ring of the polycyclic aromatic ringsystem. Preferred heteroaryl groups are those containing three to thirtycarbon atoms, preferably three to twenty carbon atoms, more preferablythree to twelve carbon atoms. Suitable heteroaryl groups includedibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene,benzofuran, benzothiophene, benzoselenophene, carbazole,indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole,triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole,thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine,oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole,indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline,isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine,phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine,phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine,preferably dibenzothiophene, dibenzofuran, dibenzoselenophene,carbazole, indolocarbazole, imidazole, pyridine, triazine,benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine,and aza-analogs thereof. Additionally, the heteroaryl group may beoptionally substituted.

Of the aryl and heteroaryl groups listed above, the groups oftriphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran,dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine,pyrazine, pyrimidine, triazine, and benzimidazole, and the respectiveaza-analogs of each thereof are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl,and heteroaryl, as used herein, are independently unsubstituted, orindependently substituted, with one or more general substituents.

In many instances, the general substituents are selected from the groupconsisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylicacid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, boryl, and combinations thereof.

In some instances, the preferred general substituents are selected fromthe group consisting of deuterium, fluorine, alkyl, cycloalkyl,heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl,and combinations thereof.

In some instances, the more preferred general substituents are selectedfrom the group consisting of deuterium, fluorine, alkyl, cycloalkyl,alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, andcombinations thereof.

In yet other instances, the most preferred general substituents areselected from the group consisting of deuterium, fluorine, alkyl,cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substitution” refer to a substituent otherthan H that is bonded to the relevant position, e.g., a carbon ornitrogen. For example, when R¹ represents mono-substitution, then one R¹must be other than H (i.e., a substitution). Similarly, when R¹represents di-substitution, then two of R¹ must be other than H.Similarly, when R¹ represents zero or no substitution, R¹, for example,can be a hydrogen for available valencies of ring atoms, as in carbonatoms for benzene and the nitrogen atom in pyrrole, or simply representsnothing for ring atoms with fully filled valencies, e.g., the nitrogenatom in pyridine. The maximum number of substitutions possible in a ringstructure will depend on the total number of available valencies in thering atoms.

As used herein, “combinations thereof” indicates that one or moremembers of the applicable list are combined to form a known orchemically stable arrangement that one of ordinary skill in the art canenvision from the applicable list. For example, an alkyl and deuteriumcan be combined to form a partial or fully deuterated alkyl group; ahalogen and alkyl can be combined to form a halogenated alkylsubstituent; and a halogen, alkyl, and aryl can be combined to form ahalogenated arylalkyl. In one instance, the term substitution includes acombination of two to four of the listed groups. In another instance,the term substitution includes a combination of two to three groups. Inyet another instance, the term substitution includes a combination oftwo groups. Preferred combinations of substituent groups are those thatcontain up to fifty atoms that are not hydrogen or deuterium, or thosewhich include up to forty atoms that are not hydrogen or deuterium, orthose that include up to thirty atoms that are not hydrogen ordeuterium. In many instances, a preferred combination of substituentgroups will include up to twenty atoms that are not hydrogen ordeuterium.

The “aza” designation in the fragments described herein, i.e.aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more ofthe C—H groups in the respective aromatic ring can be replaced by anitrogen atom, for example, and without any limitation, azatriphenyleneencompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Oneof ordinary skill in the art can readily envision other nitrogen analogsof the aza-derivatives described above, and all such analogs areintended to be encompassed by the terms as set forth herein.

As used herein, “deuterium” refers to an isotope of hydrogen. Deuteratedcompounds can be readily prepared using methods known in the art. Forexample, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, andU.S. Pat. Application Pub. No. US 2011/0037057, which are herebyincorporated by reference in their entireties, describe the making ofdeuterium-substituted organometallic complexes. Further reference ismade to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt etal., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which areincorporated by reference in their entireties, describe the deuterationof the methylene hydrogens in benzyl amines and efficient pathways toreplace aromatic ring hydrogens with deuterium, respectively.

It is to be understood that when a molecular fragment is described asbeing a substituent or otherwise attached to another moiety, its namemay be written as if it were a fragment (e.g. phenyl, phenylene,naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g.benzene, naphthalene, dibenzofuran). As used herein, these differentways of designating a substituent or attached fragment are considered tobe equivalent.

In some instance, a pair of adjacent substituents can be optionallyjoined or fused into a ring. The preferred ring is a five, six, orseven-membered carbocyclic or heterocyclic ring, includes both instanceswhere the portion of the ring formed by the pair of substituents issaturated and where the portion of the ring formed by the pair ofsubstituents is unsaturated. As used herein, “adjacent” means that thetwo substituents involved can be on the same ring next to each other, oron two neighboring rings having the two closest available substitutablepositions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in anaphthalene, as long as they can form a stable fused ring system.

B. The Compounds of the Present Disclosure

In one aspect, the present disclosure provides a compound comprising aligand L_(A) of Formula I,

In Formula I, each of Z¹, Z², Z³, Z⁴, Z⁵, and Z⁶ each independently C orN;K is selected from the group consisting of a direct bond, O, and S;when K is O or S, then Z⁶ is C;each of ring A1 and ring A2 is independently a 5-membered or 6-memberedcarbocyclic or heterocyclic rings or a multicyclic fused-ring systemcomprising more than one 5-membered or 6-membered carbocyclic orheterocyclic ring;each of R^(A) and R^(B) is independently mono, up to a maximum allowedsubstitutions, or no substitution;ligand L_(A) is coordinated to a metal M by the two indicated dashlines;M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag,and Au;M is coordinated to at least one other ligand;L_(A) can be joined with other ligands to form a tridentate,tetradentate, pentadentate, or hexadentate ligand;L¹ is an organic linker;when M is selected from the group consisting of Ru, Os, and Ir, then Kis O or S;when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au,and K is a direct bond, then M forms at least one bond to oxygen orsulfur;when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au,and K is O or S, then L¹ is selected from the group consisting of—CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—,—CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR₂—, —C(═N—)—, and —C(═CR—)—;each R^(A), R^(B), R, R′, R″ is independently a hydrogen or asubstituent selected from the group consisting of the generalsubstituents defined herein; andany two adjacent R^(A), R^(B), R, R′ and R″ can be joined or fusedtogether to form a ring.

In some embodiments, each R^(A), R^(B), R, R′, R″ is independently ahydrogen or a substituent selected from the group consisting of thepreferred general substituents defined herein. In some embodiments, eachR^(A), R^(B), R, R′, R″ is independently a hydrogen or a substituentselected from the group consisting of the more preferred generalsubstituents defined herein. In some embodiments, each R^(A), R^(B), R,R′, R″ is independently a hydrogen or a substituent selected from thegroup consisting of the most preferred general substituents definedherein.

In some embodiments, Z³ is selected from the group consisting of N andcarbene carbon.

In some embodiments, Z⁶ is C and K is O or S. In some embodiments, Z⁶ isN and K is a direct bond.

In some embodiments, ring A1 is selected from the group consisting ofimidazole, benzimidazole, imidazole-based carbene, benzimidazole-basedcarbene, pyrimidine, pyrazole, and pyridine.

In some embodiments, ring A2 is selected from the group consisting ofbenzene, pyridine, carbazole, benzimidazole, benzothiophene,dibenzothiophene, benzofuran, dibenzofuran, dibenzofluorene,naphthalene, tetrahydronaphthalene, phenoxazine, 9,10-dihydroacridine,anthracene, and phenanthrene.

In some embodiments, M is selected from the group consisting of Ru, Os,and Ir. In some embodiments, K is O. In some embodiments, K is S.

In some embodiments, M is selected from the group consisting of Pt, Pd,Cu, Ag, or Au, and K is a direct bond.

In some embodiments, the organic linker L¹ is selected from the groupconsisting of —X—, —X—X′—, —X^(L)═X^(L′)—, and —X^(L)═X^(L′)—X—, where Xand X′ are each independently selected from the group consisting of BR′,NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; and X^(L)and X^(L′) are each independently selected from the group consisting ofN and CR′.

In some embodiments, L¹ is —X—. In some embodiments, L¹ is —X—X′—. Insome embodiments, L¹ is —X^(L)═X^(L′)—. In some embodiments, L¹ is—X^(L)═X^(L′)—X—.

In some embodiments, at least one R, R′ or R″ forms a ring with one ofR^(A), R^(B), R, R′, or R″.

In some embodiments, each R, R′, and R″ is independently hydrogen or asubstituent selected from the group consisting of alkyl, cycloalkyl,aryl, and combinations thereof.

In some embodiments, M is selected from the group consisting of Pt, Pd,Cu, Ag, or Au, and K is S or O. In some such embodiments, L¹ is —CR═N—.In some such embodiments, L¹ is —CR′R″CR′R″—. In some such embodiments,L¹ is —NR′BR′—. In some such embodiments, L¹ is —CR′R″O—. In some suchembodiments, L¹ is —CR′R″S—. In some such embodiments, at least one R,R′ or R″ forms a ring with one of R^(A), R^(B), R, R′, or R″. In somesuch embodiments, each R, R′, and R″ is independently hydrogen or asubstituent selected from the group consisting of alkyl, cycloalkyl,aryl, and combinations thereof.

In some embodiments, ligand L_(A) is selected from the group consistingof the structures of the following LIST 1:

and wherein each R^(A), R^(B), R^(C), R¹, R², R³, and R⁴ isindependently a hydrogen or a substituent selected from the groupconsisting of the general substituents defined herein.

In some embodiments, ligand L_(A) is selected from the group consistingof the following structures, wherein the group will be collectivelyreferred to as L_(A,spec): L_(A)1-(Ri)(Rj)(Rk)(Rl),L_(A)2-(Ri)(Rj)(Rk)(Rl), L_(A)3-(Ri)(Rj)(Rk)(Rl),L_(A)4-(Ri)(Rj)(Rk)(Rl), L_(A)5-(Ri)(Rj)(Rk)(Rl),L_(A)6-(Ri)(Rj)(Rk)(Rl), L_(A)7-(Ri)(Rj), L_(A)8-(Ri)(Rj),L_(A)9-(Ri)(Rj), L_(A)10-(Ri)(Rj), L_(A)11-(Ri)(Rj), L_(A)12-(Ri)(Rj),L_(A)13-(Ri)(Rj), L_(A)14-(Ri)(Rj), L_(A)15-(Ri)(Rj), L_(A)16-(Ri)(Rj),L_(A)17-(Ri)(Rj), L_(A)18-(Ri)(Rj), L_(A)19-(Ri)(Rj), L_(A)20-(Ri)(Rj),L_(A)21-(Ri)(Rj), L_(A)22-(Ri)(Rj), L_(A)23-(Ri)(Rj), L_(A)24-(Ri)(Rj),L_(A)25-(Ri)(Rj), L_(A)26-(Ri)(Rj), L_(A)27-(Ri)(Rj), L_(A)28-(Ri)(Rj),L_(A)29-(Ri)(Rj), L_(A)30-(Ri)(Rj), L_(A)31-(Ri)(Rj), L_(A)32-(Ri)(Rj),L_(A)33-(Ri)(Rj), L_(A)34-(Ri)(Rj), L_(A)35-(Ri)(Rj), L_(A)36-(Ri)(Rj),L_(A)37-(Ri)(Rj), L_(A)38-(Ri)(Rj), L_(A)39-(Ri)(Rj), L_(A)40-(Ri)(Rj),L_(A)41-(Ri)(Rj)(Rk), L_(A)42-(Ri)(Rj)(Rk), L_(A)43-(Ri)(Rj),L_(A)44-(Ri)(Rj), L_(A)45-(Ri)(Rj), L_(A)46-(Ri)(Rj), L_(A)47-(Ri)(Rj),L_(A)48-(Ri)(Rj), L_(A)49-(Ri)(Rj), L_(A)50-(Ri)(Rj),L_(A)51-(Ri)(Rj)(Rk), L_(A)52-(Ri)(Rj)(Rk), L_(A)53-(Ri)(Rj)(Rk),L_(A)54-(Ri)(Rj)(Rk), L_(A)55-(Ri)(Rj)(Rk), L_(A)56-(Ri)(Rj)(Rk),L_(A)57-(Ri)(Rj)(Rk), L_(A)58-(Ri)(Rj)(Rk), L_(A)59-(Ri)(Rj)(Rk),L_(A)60-(Ri)(Rj)(Rk), L_(A)61-(Ri)(Rj)(Rk), L_(A)62-(Ri)(Rj)(Rk),L_(A)63-(Ri)(Rj)(Rk), L_(A)64-(Ri)(Rk), L_(A)65-(Ri), L_(A)66-(Ri),L_(A)67-(Ri), L_(A)68-(Ri), L_(A)69-(Ri), L_(A)70-(Ri), andL_(A)71-(Ri), wherein each of i, j, k, and l is independently an integerfrom 1 to 86, wherein the structure of each ligand L_(A) in the groupL_(A,spec) is defined by the following LIST 2:

L_(A) Structure of L_(A) Definitions L_(A)1-(Ri)(Rj(Rk)(Rl), whereL_(A)1- (R1)(R1)(R1)(R1) to L_(A)1- (R86)(R86)(R86)(R86) have thestructure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)2-(Ri)(Rj)(Rk)(Rl), where L_(A)2- (R1)(R1)(R1)(R1) to L_(A)2-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)3-(Ri)(Rj)(Rk)(Rl), L_(A)3-(R1)(R1)(R1)(R1) toL_(A)3-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)4-(Ri)(Rj)(Rk)(Rl), L_(A)4-(R1)(R1)(R1)(R1) toL_(A)4-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)5-(Ri)(Rj)(Rk)(Rl), L_(A)5-(R1)(R1)(R1)(R1) toL_(A)5-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)6-(Ri)(Rj)(Rk)(Rl), L_(A)6-(R1)(R1)(R1)(R1) toL_(A)6-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)7-(Ri)(Rj), L_(A)7-(R1)(R1) to L_(A)7- (R86)(R86) have thestructure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)8-(Ri)(Rj), L_(A)8-(R1)(R1)to L_(A)8- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)9-(Ri)(Rj), L_(A)9-(R1)(R1)to L_(A)9- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)10-(R1)(Rj),L_(A)10-(R1)(R1) to L_(A)10- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) R_(j,) L_(A)11-(Ri)(Rj),L_(A)11-(R1)(R1) to L_(A)11- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)12-(Ri)(Rj),L_(A)12-(R1)(R1) to L_(A)12- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)13-(Ri)(Rj),L_(A)13-(R1)(R1) to L_(A)13- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)14-(Ri)(Rj),L_(A)14-(R1)(R1) to L_(A)14- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)15-(Ri)(Rj),L_(A)15-(R1)(R1) to L_(A)15- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)16-(Ri)(Rj),L_(A)16-(R1)(R1) to L_(A)16- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)17-(Ri)(Rj),L_(A)17-(R1)(R1) to L_(A)17- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)18-(Ri)(Rj),L_(A)18-(R1)(R1) to L_(A)18- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)19-(Ri)(Rj),L_(A)19-(R1)(R1) to L_(A)19- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)20-(Ri)(Rj),L_(A)20-(R1)(R1) to L_(A)20- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)21-(Ri)(Rj),L_(A)21-(R1)(R1) to L_(A)21- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)22-(Ri)(Rj),L_(A)22-(R1)(R1) to L_(A)22- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)23-(Ri)(Rj),L_(A)23-(R1)(R1) to L_(A)23- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)24-(Ri)(Rj),L_(A)24-(R1)(R1) to L_(A)24- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)25-(Ri)(Rj),L_(A)25-(R1)(R1) to L_(A)25- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)26-(Ri)(Rj),L_(A)26-(R1)(R1) to L_(A)26- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)27-(Ri)(Rj),L_(A)27-(R1)(R1) to L_(A)27- (R86)(R86) have the structure,

wherein A¹ is Ri and R^(A2) is Rj, L_(A)28-(Ri)(Rj), L_(A)28-(R1)(R1) toL_(A)28- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)29-(Ri)(Rj),L_(A)29-(R1)(R1) to L_(A)29- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)30-(Ri)(Rj),L_(A)30-(R1)(R1) to L_(A)30- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)31-(Ri)(Rj),L_(A)31-(R1)(R1) to L_(A)31- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)32-(Ri)(Rj),L_(A)32-(R1)(R1) to L_(A)32- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)33-(Ri)(Rj),L_(A)33-(R1)(R1) to L_(A)33- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)34-(Ri)(Rj),L_(A)34-(R1)(R1) to L_(A)34- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)35-(Ri)(Rj),L_(A)35-(R1)(R1) to L_(A)35- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)36-(Ri)(Rj),L_(A)36-(R1)(R1) to L_(A)36- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)37-(Ri)(Rj),L_(A)37-(R1)(R1) to L_(A)37- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)38-(Ri)(Rj),L_(A)38-(R1)(R1) to L_(A)38- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)39-(Ri)(Rj),L_(A)39-(R1)(R1) to L_(A)39- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)40-(Ri)(Rj),L_(A)40-(R1)(R1) to L_(A)40- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)41-(Ri)(Rj)(Rk),L_(A)41-(R1)(R1)(R1) to L_(A)41-(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)42-(Ri)(Rj)(Rk), L_(A)42-(R1)(R1)(R1) to L_(A)42-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk, L_(A)43-(Ri)(Rj),L_(A)43-(R1)(R1) to L_(A)43- (R86)(R86) have the structure,

wherein R^(A1) is Rj and R^(A2) is Rj, L_(A)44-(Ri)(Rj),L_(A)44-(R1)(R1) to L_(A)44- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)45-(Ri)(Rj),L_(A)45-(R1)(R1) to L_(A)45- (R86)(R86) have the strcture,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)46-(Ri)(Rj),L_(A)46-(R1)(R1) to L_(A)46- (R86)(R86) have the structure,

wherein R^(A1) is Rj and R^(A2) is Rj, L_(A)47-(Ri)(Rj),L_(A)47-(R1)(R1) to L_(A)47- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)48-(Ri)(Rj),L_(A)48-(R1)(R1) to L_(A)48- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)49-(Ri)(Rj),L_(A)49-(R1)(R1) to L_(A)49- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)50-(Ri)(Rj),L_(A)50-(R1)(R1) to L_(A)50- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)51-(Ri)(Rj)(Rk),L_(A)51-(R1)(R1)(R1) to L_(A)51-(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)52-(Ri)(Rj)(Rk), L_(A)52-(R1)(R1)(R1) to L_(A)52-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)53-(Ri)(Rj)(Rk), L_(A)53-(R1)(R1)(R1) to L_(A)53-(R86)(R86)(R86)have the strucutre,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)54-(Ri)(Rj)(Rk), L_(A)54-(R1)(R1)(R1) to L_(A)54-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)55-(Ri)(Rj)(Rk), L_(A)55-(R1)(R1)(R1) to L_(A)55-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)56-(Ri)(Rj)(Rk), L_(A)56-(R1)(R1)(R1) to L_(A)56-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)57-(Ri)(Rj)(Rk), L_(A)57-(R1)(R1)(R1) to L_(A)57-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is RJ, and R^(A3) is Rk,L_(A)58-(Ri)(Rj)(Rk), L_(A)58-(R1)(R1)(R1) to L_(A)58-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)59-(Ri)(Rj)(Rk), L_(A)59-(R1)(R1)(R1) to L_(A)59-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)60-(Ri)(Rj)(Rk), L_(A)60-(R1)(R1)(R1) to L_(A)60-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)61-(Ri)(Rj)(Rk), L_(A)61-(R1)(R1)(R1) to L_(A)61-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)62-(Ri)(Rj)(Rk), L_(A)62-(R1)(R1)(R1) to L_(A)62-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)63-(Ri)(Rj)(Rk), L_(A)63-(R1)(R1)(R1) to L_(A)63-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)64-(Ri)(Rj)(Rk), L_(A)64-(R1)(R1)(R1) to L_(A)64-(R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk, L_(A)65-(Ri),L_(A)65-(R1) to L_(A)65-(R86) have the structure,

wherein R^(A1) is Ri, L_(A)66-(Ri), L_(A)66-(R1) to L_(A)66-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)67-(Ri), L_(A)67-(R1) to L_(A)67-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)68-(Ri), L_(A)68-(R1) to L_(A)68-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)69-(Ri), where L_(A)69-(R1) to L_(A)69-(R86)have the structure,

wherein R^(A1) is Ri, L_(A)70-(Ri), where L_(A)70-(R1) to L_(A)70-(R86)have the structure,

wherein R^(A1) is Ri, L_(A)71-(Ri), where L_(A)71-(R1) to L_(A)71-(R86)have the structure,

wherein R^(A1) is Ri,

wherein Ph represents phenyl; and

wherein R¹ to R⁸⁶ have the structures in the following LIST 3:

In some embodiments, the ligand L_(A) is selected from the groupconsisting of L_(A)1-(R33)(R2)(R1)(R1), L_(A)2-(R33)(R2)(R1)(R1),L_(A)1-(R33)(R6)(R1)(R1), L_(A)2-(R33)(R6)(R1)(R1),L_(A)3-(R33)(R2)(R1)(R1), L_(A)4-(R33)(R2)(R1)(R1),L_(A)1-(R49)(R2)(R1)(R1), L_(A)2-(R49)(R2)(R1)(R1),L_(A)1-(R30)(R2)(R1)(R1), L_(A)2-(R30)(R2)(R1)(R1),L_(A)1-(R30)(R6)(R1)(R1), L_(A)2-(R30)(R6)(R1)(R1),L_(A)1-(R30)(R28)(R1)(R1), L_(A)2-(R30)(R28)(R1)(R1),L_(A)1-(R33)(R28)(R1)(R1), L_(A)2-(R33)(R28)(R1)(R1), L_(A)45-(R33)(R2),L_(A)46-(R33)(R2), L_(A)9-(R33)(R1), L_(A)10-(R33)(R1),L_(A)11-(R33)(R1), L_(A)12-(R33)(R1), L_(A)13-(R33)(R1),L_(A)14-(R33)(R1), L_(A)21-(R33)(R1), L_(A)22-(R33)(R1),L_(A)33-(R33)(R1), L_(A)34-(R33)(R1), L_(A)41-(R48)(R1)(R1),L_(A)65-(R2), L_(A)66-(R2), L_(A)67-(R2), L_(A)68-(R2), L_(A)69-(R3),L_(A)70-(R3), L_(A)61-(R2)(R1)(R1), L_(A)62-(R2)(R1)(R1),L_(A)59-(R2)(R1)(R1), L_(A)59-(R3)(R1)(R1), L_(A)60-(R2)(R1)(R1),L_(A)60-(R3)(R1)(R1), L_(A)4-(R33)(R2)(R1)(R1), L_(A)43-(R33)(R2), andL_(A)44-(R33)(R2).

In some embodiments, the compound has a formula ofM(L_(A))_(p)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each abidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0,1, or 2; and p+q+r is the oxidation state of the metal M.

In some embodiments, the compound has a formula selected from the groupconsisting of Ir(L_(A))₃, Ir(L_(A))(L_(B))₂, Ir(L_(A))₂(L_(B)),Ir(L_(A))₂(L_(C)), and Ir(L_(A))(L_(B))(L_(C)); and wherein L_(A),L_(B), and L_(C) are different from each other. In some embodiments, Mis Ir, L_(B) is a substituted or unsubstituted phenylpyridine, and L_(C)is a substituted or unsubstituted acetylacetonate.

In some embodiments, the compound has a formula of Pt(L_(A))(L_(B)); andwherein L_(A) and L_(B) can be same or different. In some suchembodiments, L_(A) and L_(B) are connected to form a tetradentateligand.

In some embodiments, L_(B) and L_(C) are each independently selectedfrom the group consisting of the structures of the following LIST 4:

wherein:

T is selected from the group consisting of B, Al, Ga, and In;

each of Y¹ to Y¹³ is independently selected from the group consisting ofcarbon and nitrogen;

Y′ is selected from the group consisting of BR_(e), NR_(e), PR_(e), O,S, Se, C═O, S═O, SO₂, CR_(e)R_(f), Si_(e)R_(f), and GeR_(e)R_(f);

R_(e) and R_(f) can be fused or joined to form a ring;

each R_(a), R_(b), R_(c), and R_(d) independently represents zero, mono,or up to a maximum allowed number of substitutions to its associatedring;

each of R_(a1), R_(b1), R_(c1), R_(d1), R_(a), R_(b), R_(c), R_(d),R_(e) and R_(f) is independently a hydrogen or a substituent selectedfrom the group consisting of the general substituents defined herein;and

any two adjacent R_(a), R_(b), R_(c), R_(d), R_(e) and R_(f) can befused or joined to form a ring or form a multidentate ligand.

In some embodiments, L_(B) and L_(C) are each independently selectedfrom the group consisting of the structures of the following LIST 5:

wherein: R_(a)′, R_(b)′, R_(c)′, R_(d)′, R_(e)′, R_(f)′, R_(g)′, andR_(n)′ each independently represents zero, mono, or up to a maximumallowed substitution to its associated ring; each of R_(a1), R_(b1),R_(c1), R_(a), R_(b), R_(c), R_(a)′, R_(b)′, R_(c)′, R_(d)′, R_(f)′,R_(g)′, and R_(n)′ is independently hydrogen or a substituent selectedfrom the group consisting of the preferred general substituents definedherein; and two adjacent R_(a)′, R_(b)′, R_(c)′, R_(d)′, R_(e)′, R_(f)′,R_(g)′, and R_(n)′ can be fused or joined to form a ring or form amultidentate ligand.

In some embodiments, when the compound has formula Ir(L_(A))₃, L_(A) isselected from the group consisting of the structures in the groupL_(A,spec), and the compound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₃ to Ir(L_(A)71-(R86))₃. Using thenomenclature for each of the ligand L_(A) in the group L_(A,spec), thegroup of compounds consisting of Ir(L_(A)1-(R1)(R1)(R1)(R1))₃ toIr(L_(A)71-(R86))₃ can also be written as Ir(L_(A)1-(R1)(R1)(R1)(R1))₃to Ir(L_(A)1-(R86)(R86)(R86)(R86))₃, Ir(L_(A)2-(R1)(R1)(R1)(R1))₃ toIr(L_(A)2-(R86)(R86)(R86)(R86))₃, Ir(L_(A)3-(R1)(R1)(R1)(R1))₃ toIr(L_(A)3-(R86)(R86)(R86)(R86))₃, Ir(L_(A)4-(R1)(R1)(R1)(R1))₃ toIr(L_(A)4-(R86)(R86)(R86)(R86))₃, Ir(L_(A)5-(R1)(R1)(R1)(R1))₃ toIr(L_(A)5-(R86)(R86)(R86)(R86))₃, Ir(L_(A)6-(R1)(R1)(R1)(R1))₃ toIr(L_(A)6-(R86)(R86)(R86)(R86))₃, Ir(L_(A)7-(R1)(R1))₃ toIr(L_(A)7-(R86)(R86))₃, Ir(L_(A)8-(R1)(R1))₃ to Ir(L_(A)8-(R86)(R86))₃,Ir(L_(A)9-(R1)(R1))₃ to Ir(L_(A)9-(R86)(R86))₃, Ir(L_(A)10-(R1)(R1))₃ toIr(L_(A)10-(R86)(R86))₃, Ir(L_(A)11-(R1)(R1))₃ toIr(L_(A)11-(R86)(R86))₃, Ir(L_(A)12-(R1)(R1))₃ toIr(L_(A)12-(R86)(R86))₃, Ir(L_(A)13-(R1)(R1))₃ toIr(L_(A)13-(R86)(R86))₃, Ir(L_(A)14-(R1)(R1))₃ toIr(L_(A)14-(R86)(R86))₃, Ir(L_(A)15-(R1)(R1))₃ toIr(L_(A)15-(R86)(R86))₃, Ir(L_(A)16-(R1)(R1))₃ toIr(L_(A)16-(R86)(R86))₃, Ir(L_(A)17-(R1)(R1))₃ toIr(L_(A)17-(R86)(R86))₃, Ir(L_(A)18-(R1)(R1))₃ toIr(L_(A)18-(R86)(R86))₃, Ir(L_(A)19-(R1)(R1))₃ toIr(L_(A)19-(R86)(R86))₃, Ir(L_(A)20-(R1)(R1))₃ toIr(L_(A)20-(R86)(R86))₃, Ir(L_(A)21-(R1)(R1))₃ toIr(L_(A)21-(R86)(R86))₃, Ir(L_(A)22-(R1)(R1))₃ toIr(L_(A)22-(R86)(R86))₃, Ir(L_(A)23-(R1)(R1))₃ toIr(L_(A)23-(R86)(R86))₃, Ir(L_(A)24-(R1)(R1))₃ toIr(L_(A)24-(R86)(R86))₃, Ir(L_(A)25-(R1)(R1)₃ to Ir(L_(A)25-(R86)(R86)₃,Ir(L_(A)26-(R1)(R1))₃ to Ir(L_(A)26-(R86)(R86))₃, Ir(L_(A)27-(R1)(R1))₃to Ir(L_(A)27-(R86)(R86))₃, Ir(L_(A)28-(R1)(R1))₃ toIr(L_(A)28-(R86)(R86))₃, Ir(L_(A)29-(R1)(R1))₃ toIr(L_(A)29-(R86)(R86))₃, Ir(L_(A)30-(R1)(R1))₃ toIr(L_(A)30-(R86)(R86))₃, Ir(L_(A)31-(R1)(R1))₃ toIr(L_(A)31-(R86)(R86))₃, Ir(L_(A)32-(R1)(R1))₃ toIr(L_(A)32-(R86)(R86))₃, Ir(L_(A)33-(R1)(R1))₃ toIr(L_(A)33-(R86)(R86))₃, Ir(L_(A)34-(R1)(R1))₃ toIr(L_(A)34-(R86)(R86))₃, Ir(L_(A)35-(R1)(R1))₃ toIr(L_(A)35-(R86)(R86))₃, Ir(L_(A)36-(R1)(R1))₃ toIr(L_(A)36-(R86)(R86))₃, Ir(L_(A)37-(R1)(R1))₃ toIr(L_(A)37-(R86)(R86))₃, Ir(L_(A)38-(R1)(R1))₃ toIr(L_(A)38-(R86)(R86))₃, Ir(L_(A)39-(R1)(R1))₃ toIr(L_(A)39-(R86)(R86))₃, Ir(L_(A)40-(R1)(R1))₃ toIr(L_(A)40-(R86)(R86))₃, Ir(L_(A)41-(R1)(R1)(R1))₃ toIr(L_(A)41-(R86)(R86)(R86))₃, Ir(L_(A)42-(R1)(R1)(R1))₃ toIr(L_(A)42-(R86)(R86)(R86))₃, Ir(L_(A)43-(R1)(R1))₃ toIr(L_(A)43-(R86)(R86))₃, Ir(L_(A)44-(R1)(R1))₃ toIr(L_(A)44-(R86)(R86))₃, Ir(L_(A)45-(R1)(R1))₃ toIr(L_(A)45-(R86)(R86))₃, Ir(L_(A)46-(R1)(R1))₃ toIr(L_(A)46-(R86)(R86))₃, Ir(L_(A)47-(R1)(R1))₃ toIr(L_(A)47-(R86)(R86))₃, Ir(L_(A)48-(R1)(R1))₃ toIr(L_(A)48-(R86)(R86))₃, Ir(L_(A)49-(R1)(R1))₃ toIr(L_(A)49-(R86)(R86))₃, Ir(L_(A)50-(R1)(R1))₃ toIr(L_(A)50-(R86)(R86))₃, Ir(L_(A)51-(R1)(R1)(R1))₃ toIr(L_(A)51-(R86)(R86)(R86))₃, Ir(L_(A)52-(R1)(R1)(R1))₃ toIr(L_(A)52-(R86)(R86)(R86))₃, Ir(L_(A)53-(R1)(R1)(R1))₃ toIr(L_(A)53-(R86)(R86)(R86))₃, Ir(L_(A)54-(R1)(R1)(R1))₃ toIr(L_(A)54-(R86)(R86)(R86))₃, Ir(L_(A)55-(R1)(R1)(R1))₃ toIr(L_(A)55-(R86)(R86)(R86))₃, Ir(L_(A)56-(R1)(R1)(R1))₃ toIr(L_(A)56-(R86)(R86)(R86))₃, Ir(L_(A)57-(R1)(R1)(R1))₃ toIr(L_(A)57-(R86)(R86)(R86))₃, Ir(L_(A)58-(R1)(R1)(R1))₃ toIr(L_(A)58-(R86)(R86)(R86))₃, Ir(L_(A)59-(R1)(R1)(R1))₃ toIr(L_(A)59-(R86)(R86)(R86))₃, Ir(L_(A)60-(R1)(R1)(R1))₃ toIr(L_(A)60-(R86)(R86)(R86))₃, Ir(L_(A)61-(R1)(R1)(R1))₃ toIr(L_(A)61-(R86)(R86)(R86))₃, Ir(L_(A)62-(R1)(R1)(R1))₃ toIr(L_(A)62-(R86)(R86)(R86))₃, Ir(L_(A)63-(R1)(R1)(R1))₃ toIr(L_(A)63-(R86)(R86)(R86))₃, Ir(L_(A)64-(R1)(R1)(R1))₃ toIr(L_(A)64-(R86)(R86)(R86))₃, Ir(L_(A)65-(R1))₃ to Ir(L_(A)65-(R86))₃,Ir(L_(A)66-(R1))₃ to Ir(L_(A)66-(R86))₃, Ir(L_(A)67-(R1))₃ toIr(L_(A)67-(R86))₃, Ir(L_(A)68-(R1))₃ to Ir(L_(A)68-(R86))₃,Ir(L_(A)69-(R1))₃ to Ir(L_(A)69-(R86))₃, Ir(L_(A)70-(R1))₃ toIr(L_(A)70-(R86))₃, and Ir(L_(A)71-(R1))₃ to Ir(L_(A)71-(R86))₃.

In some embodiments, when the compound has formula Ir(L_(A))(L_(Bk))₂,L_(A) is selected from the group consisting of the structures ofL_(A,spec); where k is an integer from 1 to 540; and the compound isselected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1)(L_(B1))₂ to Ir(L_(A)71-(R86))(L_(B540))₂,wherein each of the compounds in the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1)(L_(B1))₂ to Ir(L_(A)71-(R86)(L_(B540))₂ canbe written using the nomenclature for each of the ligand L_(A) in thegroup L_(A,spec), in the similar manner shown above for the compound offormula Ir(L_(A))₃.

In some embodiments, when the compound has formula Ir(L_(A))₂(L_(Bk)),L_(A) is selected from the group consisting of the structures ofL_(A,spec); where k is an integer from 1 to 540; and the compound isselected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(B1)) to Ir(L_(A)71-(R86))₂(L_(B540)),wherein each of the compounds in the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(B1)) to Ir(L_(A)71-(R86))₂(L_(B540)) canbe written using the nomenclature for each of the ligand L_(A) in thegroup L_(A,spec), in the similar manner shown above for the compound offormula Ir(L_(A))₃.

In some embodiments, when the compound has formula Ir(L_(A))₂(L_(Cj-1)),L_(A) is selected from the group consisting of the structures ofL_(A,spec); where j is an integer from 1 to 1416; and the compound isselected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(C1-I)) to Ir(L_(A)71-(R86)(L_(C1416-I)),wherein each of the compounds in the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(C1-I)) to Ir(L_(A)71-(R86)(L_(C1416-I))can be written using the nomenclature for each of the ligand L_(A) inthe group L_(A,spec), in the similar manner shown above for the compoundof formula Ir(L_(A))₃.

In some embodiments, when the compound has formulaIr(L_(A))₂(L_(Cj-II)), L_(A) is selected from the group consisting ofthe structures of L_(A,spec); where j is an integer from 1 to 1416; andthe compound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(C1-II)) toIr(L_(A)71-(R86)(L_(C1416-II)), wherein each of the compounds in thegroup consisting of Ir(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(C1-II)) toIr(L_(A)71-(R86)(L_(C1416-II)) can be written using the nomenclature foreach of the ligand L_(A) in the group L_(A,spec), in the similar mannershown above for the compound of formula Ir(L_(A))₃.

In each of the embodiments of the compound disclosed herein where thecompound includes one or more ligand L_(Bk) where k is an integer from 1to 540, each L_(Bk) has the structure defined in the following LIST 6:

In each of the embodiments of the compounds disclosed herein where thecompound includes one or more ligands L_(Cj-I) and/or L_(Cj-II) where jis an integer from 1 to 1416, each L_(Cj-I) has a structure based onformula

andeach L_(Cj-II) has a structure based on formula

wherein for each LG in L_(Cj) in L_(Cj-I) and L_(Cj-II), R²⁰¹ and R²⁰are each independently defined in the following LIST 7:

L_(Cj) R²⁰¹ R²⁰² L_(C1) R^(D1) R^(D1) L_(C2) R^(D2) R^(D2) L_(C3) R^(D3)R^(D3) L_(C4) R^(D4) R^(D4) L_(C5) R^(D5) R^(D5) L_(C6) R^(D6) R^(D6)L_(C7) R^(D7) R^(D7) L_(C8) R^(D8) R^(D8) L_(C9) R^(D9) R^(D9) L_(C10)R^(D10) R^(D10) L_(C11) R^(D11) R^(D11) L_(C12) R^(D12) R^(D12) L_(C13)R^(D13) R^(D13) L_(C14) R^(D14) R^(D14) L_(C15) R^(D15) R^(D15) L_(C16)R^(D16) R^(D16) L_(C17) R^(D17) R^(D17) L_(C18) R^(D18) R^(D18) L_(C19)R^(D19) R^(D19) L_(C20) R^(D20) R^(D20) L_(C21) R^(D21) R^(D21) L_(C22)R^(D22) R^(D22) L_(C23) R^(D23) R^(D23) L_(C24) R^(D24) R^(D24) L_(C25)R^(D25) R^(D25) L_(C26) R^(D26) R^(D26) L_(C27) R^(D27) R^(D27) L_(C28)R^(D28) R^(D28) L_(C29) R^(D29) R^(D29) L_(C30) R^(D30) R^(D30) L_(C31)R^(D31) R^(D31) L_(C32) R^(D32) R^(D32) L_(C33) R^(D33) R^(D33) L_(C34)R^(D34) R^(D34) L_(C35) R^(D35) R^(D35) L_(C36) R^(D36) R^(D36) L_(C37)R^(D37) R^(D37) L_(C38) R^(D38) R^(D38) L_(C39) R^(D39) R^(D39) L_(C40)R^(D40) R^(D40) L_(C41) R^(D41) R^(D41) L_(C42) R^(D42) R^(D42) L_(C43)R^(D43) R^(D43) L_(C44) R^(D44) R^(D44) L_(C45) R^(D45) R^(D45) L_(C46)R^(D46) R^(D46) L_(C47) R^(D47) R^(D47) L_(C48) R^(D48) R^(D48) L_(C49)R^(D49) R^(D49) L_(C50) R^(D50) R^(D50) L_(C51) R^(D51) R^(D51) L_(C52)R^(D52) R^(D52) L_(C53) R^(D53) R^(D53) L_(C54) R^(D54) R^(D54) L_(C55)R^(D55) R^(D55) L_(C56) R^(D56) R^(D56) L_(C57) R^(D57) R^(D57) L_(C58)R^(D58) R^(D58) L_(C59) R^(D59) R^(D59) L_(C60) R^(D60) R^(D60) L_(C61)R^(D61) R^(D61) L_(C62) R^(D62) R^(D62) L_(C63) R^(D63) R^(D63) L_(C64)R^(D64) R^(D64) L_(C65) R^(D65) R^(D65) L_(C66) R^(D66) R^(D66) L_(C67)R^(D67) R^(D67) L_(C68) R^(D68) R^(D68) L_(C69) R^(D69) R^(D69) L_(C70)R^(D70) R^(D70) L_(C71) R^(D71) R^(D71) L_(C72) R^(D72) R^(D72) L_(C73)R^(D73) R^(D73) L_(C74) R^(D74) R^(D74) L_(C75) R^(D75) R^(D75) L_(C76)R^(D76) R^(D76) L_(C77) R^(D77) R^(D77) L_(C78) R^(D78) R^(D78) L_(C79)R^(D79) R^(D79) L_(C80) R^(D80) R^(D80) L_(C81) R^(D81) R^(D81) L_(C82)R^(D82) R^(D82) L_(C83) R^(D83) R^(D83) L_(C84) R^(D84) R^(D84) L_(C85)R^(D85) R^(D85) L_(C86) R^(D86) R^(D86) L_(C87) R^(D87) R^(D87) L_(C88)R^(D88) R^(D88) L_(C89) R^(D89) R^(D89) L_(C90) R^(D90) R^(D90) L_(C91)R^(D91) R^(D91) L_(C92) R^(D92) R^(D92) L_(C93) R^(D93) R^(D93) L_(C94)R^(D94) R^(D94) L_(C95) R^(D95) R^(D95) L_(C96) R^(D96) R^(D96) L_(C97)R^(D97) R^(D97) L_(C98) R^(D98) R^(D98) L_(C99) R^(D99) R^(D99) L_(C100)R^(D100) R^(D100) L_(C101) R^(D101) R^(D101) L_(C102) R^(D102) R^(D102)L_(C103) R^(D103) R^(D103) L_(C104) R^(D104) R^(D104) L_(C105) R^(D105)R^(D105) L_(C106) R^(D106) R^(D106) L_(C107) R^(D107) R^(D107) L_(C108)R^(D108) R^(D108) L_(C109) R^(D109) R^(D109) L_(C110) R^(D110) R^(D110)L_(C111) R^(D111) R^(D111) L_(C112) R^(D112) R^(D112) L_(C113) R^(D113)R^(D113) L_(C114) R^(D114) R^(D114) L_(C115) R^(D115) R^(D115) L_(C116)R^(D116) R^(D116) L_(C117) R^(D117) R^(D117) L_(C118) R^(D118) R^(D118)L_(C119) R^(D119) R^(D119) L_(C120) R^(D120) R^(D120) L_(C121) R^(D121)R^(D121) L_(C122) R^(D122) R^(D122) L_(C123) R^(D123) R^(D123) L_(C124)R^(D124) R^(D124) L_(C125) R^(D125) R^(D125) L_(C126) R^(D126) R^(D126)L_(C127) R^(D127) R^(D127) L_(C128) R^(D128) R^(D128) L_(C129) R^(D129)R^(D129) L_(C130) R^(D130) R^(D130) L_(C131) R^(D131) R^(D131) L_(C132)R^(D132) R^(D132) L_(C133) R^(D133) R^(D133) L_(C134) R^(D134) R^(D134)L_(C135) R^(D135) R^(D135) L_(C136) R^(D136) R^(D136) L_(C137) R^(D137)R^(D137) L_(C138) R^(D138) R^(D138) L_(C139) R^(D139) R^(D139) L_(C140)R^(D140) R^(D140) L_(C141) R^(D141) R^(D141) L_(C142) R^(D142) R^(D142)L_(C143) R^(D143) R^(D143) L_(C144) R^(D144) R^(D144) L_(C145) R^(D145)R^(D145) L_(C146) R^(D146) R^(D146) L_(C147) R^(D147) R^(D147) L_(C148)R^(D148) R^(D148) L_(C149) R^(D149) R^(D149) L_(C150) R^(D150) R^(D150)L_(C151) R^(D151) R^(D151) L_(C152) R^(D152) R^(D152) L_(C153) R^(D153)R^(D153) L_(C154) R^(D154) R^(D154) L_(C155) R^(D155) R^(D155) L_(C156)R^(D156) R^(D156) L_(C157) R^(D157) R^(D157) L_(C158) R^(D158) R^(D158)L_(C159) R^(D159) R^(D159) L_(C160) R^(D160) R^(D160) L_(C161) R^(D161)R^(D161) L_(C162) R^(D162) R^(D162) L_(C163) R^(D163) R^(D163) L_(C164)R^(D164) R^(D164) L_(C165) R^(D165) R^(D165) L_(C166) R^(D166) R^(D166)L_(C167) R^(D167) R^(D167) L_(C168) R^(D168) R^(D168) L_(C169) R^(D169)R^(D169) L_(C170) R^(D170) R^(D170) L_(C171) R^(D171) R^(D171) L_(C172)R^(D172) R^(D172) L_(C173) R^(D173) R^(D173) L_(C174) R^(D174) R^(D174)L_(C175) R^(D175) R^(D175) L_(C176) R^(D176) R^(D176) L_(C177) R^(D177)R^(D177) L_(C178) R^(D178) R^(D178) L_(C179) R^(D179) R^(D179) L_(C180)R^(D180) R^(D180) L_(C181) R^(D181) R^(D181) L_(C182) R^(D182) R^(D182)L_(C183) R^(D183) R^(D183) L_(C184) R^(D184) R^(D184) L_(C185) R^(D185)R^(D185) L_(C186) R^(D186) R^(D186) L_(C187) R^(D187) R^(D187) L_(C188)R^(D188) R^(D188) L_(C189) R^(D189) R^(D189) L_(C190) R^(D190) R^(D190)L_(C191) R^(D191) R^(D191) L_(C192) R^(D192) R^(D192) L_(C193) R^(D1)R^(D3) L_(C194) R^(D1) R^(D4) L_(C195) R^(D1) R^(D5) L_(C196) R^(D1)R^(D9) L_(C197) R^(D1) R^(D10) L_(C198) R^(D1) R^(D17) L_(C199) R^(D1)R^(D18) L_(C200) R^(D1) R^(D20) L_(C201) R^(D1) R^(D22) L_(C202) R^(D1)R^(D37) L_(C203) R^(D1) R^(D40) L_(C204) R^(D1) R^(D41) L_(C205) R^(D1)R^(D42) L_(C206) R^(D1) R^(D43) L_(C207) R^(D1) R^(D48) L_(C208) R^(D1)R^(D49) L_(C209) R^(D1) R^(D50) L_(C210) R^(D1) R^(D54) L_(C211) R^(D1)R^(D55) L_(C212) R^(D1) R^(D58) L_(C213) R^(D1) R^(D59) L_(C214) R^(D1)R^(D78) L_(C215) R^(D1) R^(D79) L_(C216) R^(D1) R^(D81) L_(C217) R^(D1)R^(D87) L_(C218) R^(D1) R^(D88) L_(C219) R^(D1) R^(D89) L_(C220) R^(D1)R^(D93) L_(C221) R^(D1) R^(D116) L_(C222) R^(D1) R^(D117) L_(C223)R^(D1) R^(D118) L_(C224) R^(D1) R^(D119) L_(C225) R^(D1) R^(D120)L_(C226) R^(D1) R^(D133) L_(C227) R^(D1) R^(D134) L_(C228) R^(D1)R^(D135) L_(C229) R^(D1) R^(D136) L_(C230) R^(D1) R^(D143) L_(C231)R^(D1) R^(D144) L_(C232) R^(D1) R^(D145) L_(C233) R^(D1) R^(D146)L_(C234) R^(D1) R^(D147) L_(C235) R^(D1) R^(D149) L_(C236) R^(D1)R^(D151) L_(C237) R^(D1) R^(D154) L_(C238) R^(D1) R^(D155) L_(C239)R^(D1) R^(D161) L_(C240) R^(D1) R^(D175) L_(C241) R^(D4) R^(D3) L_(C242)R^(D4) R^(D5) L_(C243) R^(D4) R^(D9) L_(C244) R^(D4) R^(D10) L_(C245)R^(D4) R^(D17) L_(C246) R^(D4) R^(D18) L_(C247) R^(D4) R^(D20) L_(C248)R^(D4) R^(D22) L_(C249) R^(D4) R^(D37) L_(C250) R^(D4) R^(D40) L_(C251)R^(D4) R^(D41) L_(C252) R^(D4) R^(D42) L_(C253) R^(D4) R^(D43) L_(C254)R^(D4) R^(D48) L_(C255) R^(D4) R^(D49) L_(C256) R^(D4) R^(D50) L_(C257)R^(D4) R^(D54) L_(C258) R^(D4) R^(D55) L_(C259) R^(D4) R^(D58) L_(C260)R^(D4) R^(D59) L_(C261) R^(D4) R^(D78) L_(C262) R^(D4) R^(D79) L_(C263)R^(D4) R^(D81) L_(C264) R^(D4) R^(D87) L_(C265) R^(D4) R^(D88) L_(C266)R^(D4) R^(D89) L_(C267) R^(D4) R^(D93) L_(C268) R^(D4) R^(D116) L_(C269)R^(D4) R^(D117) L_(C270) R^(D4) R^(D118) L_(C271) R^(D4) R^(D119)L_(C272) R^(D4) R^(D120) L_(C273) R^(D4) R^(D133) L_(C274) R^(D4)R^(D134) L_(C275) R^(D4) R^(D135) L_(C276) R^(D4) R^(D136) L_(C277)R^(D4) R^(D143) L_(C278) R^(D4) R^(D144) L_(C279) R^(D4) R^(D145)L_(C280) R^(D4) R^(D146) L_(C281) R^(D4) R^(D147) L_(C282) R^(D4)R^(D149) L_(C283) R^(D4) R^(D151) L_(C284) R^(D4) R^(D154) L_(C285)R^(D4) R^(D155) L_(C286) R^(D4) R^(D161) L_(C287) R^(D4) R^(D175)L_(C288) R^(D9) R^(D3) L_(C289) R^(D9) R^(D5) L_(C290) R^(D9) R^(D10)L_(C291) R^(D9) R^(D17) L_(C292) R^(D9) R^(D18) L_(C293) R^(D9) R^(D20)L_(C294) R^(D9) R^(D22) L_(C295) R^(D9) R^(D37) L_(C296) R^(D9) R^(D40)L_(C297) R^(D9) R^(D41) L_(C298) R^(D9) R^(D42) L_(C299) R^(D9) R^(D43)L_(C300) R^(D9) R^(D48) L_(C301) R^(D9) R^(D49) L_(C302) R^(D9) R^(D50)L_(C303) R^(D9) R^(D54) L_(C304) R^(D9) R^(D55) L_(C305) R^(D9) R^(D58)L_(C306) R^(D9) R^(D59) L_(C307) R^(D9) R^(D78) L_(C308) R^(D9) R^(D79)L_(C309) R^(D9) R^(D81) L_(C310) R^(D9) R^(D87) L_(C311) R^(D9) R^(D88)L_(C312) R^(D9) R^(D89) L_(C313) R^(D9) R^(D93) L_(C314) R^(D9) R^(D116)L_(C315) R^(D9) R^(D117) L_(C316) R^(D9) R^(D118) L_(C317) R^(D9)R^(D119) L_(C318) R^(D9) R^(D120) L_(C319) R^(D9) R^(D133) L_(C320)R^(D9) R^(D134) L_(C321) R^(D9) R^(D135) L_(C322) R^(D9) R^(D136)L_(C323) R^(D9) R^(D143) L_(C324) R^(D9) R^(D144) L_(C325) R^(D9)R^(D145) L_(C326) R^(D9) R^(D146) L_(C327) R^(D9) R^(D147) L_(C328)R^(D9) R^(D149) L_(C329) R^(D9) R^(D151) L_(C330) R^(D9) R^(D154)L_(C331) R^(D9) R^(D155) L_(C332) R^(D9) R^(D161) L_(C333) R^(D9)R^(D175) L_(C334) R^(D10) R^(D3) L_(C335) R^(D10) R^(D5) L_(C336)R^(D10) R^(D17) L_(C337) R^(D10) R^(D18) L_(C338) R^(D10) R^(D20)L_(C339) R^(D10) R^(D22) L_(C340) R^(D10) R^(D37) L_(C341) R^(D10)R^(D40) L_(C342) R^(D10) R^(D41) L_(C343) R^(D10) R^(D42) L_(C344)R^(D10) R^(D43) L_(C345) R^(D10) R^(D48) L_(C346) R^(D10) R^(D49)L_(C347) R^(D10) R^(D50) L_(C348) R^(D10) R^(D54) L_(C349) R^(D10)R^(D55) L_(C350) R^(D10) R^(D58) L_(C351) R^(D10) R^(D59) L_(C352)R^(D10) R^(D78) L_(C353) R^(D10) R^(D79) L_(C354) R^(D10) R^(D81)L_(C355) R^(D10) R^(D87) L_(C356) R^(D10) R^(D88) L_(C357) R^(D10)R^(D89) L_(C358) R^(D10) R^(D93) L_(C359) R^(D10) R^(D116) L_(C360)R^(D10) R^(D117) L_(C361) R^(D10) R^(D118) L_(C362) R^(D10) R^(D119)L_(C363) R^(D10) R^(D120) L_(C364) R^(D10) R^(D133) L_(C365) R^(D10)R^(D14) L_(C366) R^(D10) R^(D135) L_(C367) R^(D10) R^(D136) L_(C368)R^(D10) R^(D143) L_(C369) R^(D10) R^(D144) L_(C370) R^(D10) R^(D145)L_(C371) R^(D10) R^(D146) L_(C372) R^(D10) R^(D147) L_(C373) R^(D10)R^(D149) L_(C374) R^(D10) R^(D151) L_(C375) R^(D10) R^(D154) L_(C376)R^(D10) R^(D155) L_(C377) R^(D10) R^(D161) L_(C378) R^(D10) R^(D175)L_(C379) R^(D17) R^(D3) L_(C380) R^(D17) R^(D5) L_(C381) R^(D17) R^(D18)L_(C382) R^(D17) R^(D20) L_(C383) R^(D17) R^(D22) L_(C384) R^(D17)R^(D37) L_(C385) R^(D17) R^(D40) L_(C386) R^(D17) R^(D41) L_(C387)R^(D17) R^(D42) L_(C388) R^(D17) R^(D43) L_(C389) R^(D17) R^(D48)L_(C390) R^(D17) R^(D49) L_(C391) R^(D17) R^(D50) L_(C392) R^(D17)R^(D54) L_(C393) R^(D17) R^(D55) L_(C394) R^(D17) R^(D58) L_(C395)R^(D17) R^(D59) L_(C396) R^(D17) R^(D78) L_(C397) R^(D17) R^(D79)L_(C398) R^(D17) R^(D81) L_(C399) R^(D17) R^(D87) L_(C400) R^(D17)R^(D88) L_(C401) R^(D17) R^(D89) L_(C402) R^(D17) R^(D93) L_(C403)R^(D17) R^(D116) L_(C404) R^(D17) R^(D117) L_(C405) R^(D17) R^(D118)L_(C406) R^(D17) R^(D119) L_(C407) R^(D17) R^(D120) L_(C408) R^(D17)R^(D133) L_(C409) R^(D17) R^(D134) L_(C410) R^(D17) R^(D135) L_(C411)R^(D17) R^(D136) L_(C412) R^(D17) R^(D143) L_(C413) R^(D17) R^(D144)L_(C414) R^(D17) R^(D145) L_(C415) R^(D17) R^(D146) L_(C416) R^(D17)R^(D147) L_(C417) R^(D17) R^(D149) L_(C418) R^(D17) R^(D151) L_(C419)R^(D17) R^(D154) L_(C420) R^(D17) R^(D155) L_(C421) R^(D17) R^(D161)L_(C422) R^(D17) R^(D175) L_(C423) R^(D50) R^(D3) L_(C424) R^(D50)R^(D5) L_(C425) R^(D50) R^(D18) L_(C426) R^(D50) R^(D20) L_(C427)R^(D50) R^(D22) L_(C428) R^(D50) R^(D37) L_(C429) R^(D50) R^(D40)L_(C430) R^(D50) R^(D41) L_(C431) R^(D50) R^(D42) L_(C432) R^(D50)R^(D43) L_(C433) R^(D50) R^(D48) L_(C434) R^(D50) R^(D49) L_(C435)R^(D50) R^(D54) L_(C436) R^(D50) R^(D55) L_(C437) R^(D50) R^(D58)L_(C438) R^(D50) R^(D59) L_(C439) R^(D50) R^(D78) L_(C440) R^(D50)R^(D79) L_(C441) R^(D50) R^(D81) L_(C442) R^(D50) R^(D87) L_(C443)R^(D50) R^(D88) L_(C444) R^(D50) R^(D89) L_(C445) R^(D50) R^(D93)L_(C446) R^(D50) R^(D116) L_(C447) R^(D50) R^(D117) L_(C448) R^(D50)R^(D118) L_(C449) R^(D50) R^(D119) L_(C450) R^(D50) R^(D120) L_(C451)R^(D50) R^(D133) L_(C452) R^(D50) R^(D134) L_(C453) R^(D50) R^(D135)L_(C454) R^(D50) R^(D136) L_(C455) R^(D50) R^(D143) L_(C456) R^(D50)R^(D144) L_(C457) R^(D50) R^(D145) L_(C458) R^(D50) R^(D146) L_(C459)R^(D50) R^(D147) L_(C460) R^(D50) R^(D149) L_(C461) R^(D50) R^(D151)L_(C462) R^(D50) R^(D154) L_(C463) R^(D50) R^(D155) L_(C464) R^(D50)R^(D161) L_(C465) R^(D50) R^(D175) L_(C466) R^(D55) R^(D3) L_(C467)R^(D55) R^(D5) L_(C468) R^(D55) R^(D18) L_(C469) R^(D55) R^(D20)L_(C470) R^(D55) R^(D22) L_(C471) R^(D55) R^(D37) L_(C472) R^(D55)R^(D40) L_(C473) R^(D55) R^(D41) L_(C474) R^(D55) R^(D42) L_(C475)R^(D55) R^(D42) L_(C476) R^(D55) R^(D48) L_(C477) R^(D55) R^(D49)L_(C478) R^(D55) R^(D54) L_(C479) R^(D55) R^(D58) L_(C480) R^(D55)R^(D59) L_(C481) R^(D55) R^(D78) L_(C482) R^(D55) R^(D79) L_(C483)R^(D55) R^(D81) L_(C484) R^(D55) R^(D87) L_(C485) R^(D55) R^(D88)L_(C486) R^(D55) R^(D89) L_(C487) R^(D55) R^(D93) L_(C488) R^(D55)R^(D116) L_(C489) R^(D55) R^(D117) L_(C490) R^(D55) R^(D118) L_(C491)R^(D55) R^(D119) L_(C492) R^(D55) R^(D120) L_(C493) R^(D55) R^(D133)L_(C494) R^(D55) R^(D134) L_(C495) R^(D55) R^(D135) L_(C496) R^(D55)R^(D136) L_(C497) R^(D55) R^(D143) L_(C498) R^(D55) R^(D144) L_(C499)R^(D55) R^(D145) L_(C500) R^(D55) R^(D146) L_(C501) R^(D55) R^(D147)L_(C502) R^(D55) R^(D149) L_(C503) R^(D55) R^(D151) L_(C504) R^(D55)R^(D154) L_(C505) R^(D55) R^(D155) L_(C506) R^(D55) R^(D161) L_(C507)R^(D55) R^(D175) L_(C508) R^(D116) R^(D3) L_(C509) R^(D116) R^(D5)L_(C510) R^(D116) R^(D17) L_(C511) R^(D116) R^(D18) L_(C512) R^(D116)R^(D20) L_(C513) R^(D116) R^(D22) L_(C514) R^(D116) R^(D37) L_(C515)R^(D116) R^(D40) L_(C516) R^(D116) R^(D41) L_(C517) R^(D116) R^(D42)L_(C518) R^(D116) R^(D43) L_(C519) R^(D116) R^(D48) L_(C520) R^(D116)R^(D49) L_(C521) R^(D116) R^(D54) L_(C522) R^(D116) R^(D58) L_(C523)R^(D116) R^(D59) L_(C524) R^(D116) R^(D78) L_(C525) R^(D116) R^(D79)L_(C526) R^(D116) R^(D81) L_(C527) R^(D116) R^(D87) L_(C528) R^(D116)R^(D88) L_(C529) R^(D116) R^(D89) L_(C530) R^(D116) R^(D93) L_(C531)R^(D116) R^(D117) L_(C532) R^(D116) R^(D118) L_(C533) R^(D116) R^(D119)L_(C534) R^(D116) R^(D120) L_(C535) R^(D116) R^(D133) L_(C536) R^(D116)R^(D134) L_(C537) R^(D116) R^(D135) L_(C538) R^(D116) R^(D136) L_(C539)R^(D116) R^(D143) L_(C540) R^(D116) R^(D144) L_(C541) R^(D116) R^(D145)L_(C542) R^(D116) R^(D146) L_(C543) R^(D116) R^(D147) L_(C544) R^(D116)R^(D149) L_(C545) R^(D116) R^(D151) L_(C546) R^(D116) R^(D154) L_(C547)R^(D116) R^(D155) L_(C548) R^(D116) R^(D161) L_(C549) R^(D116) R^(D175)L_(C550) R^(D143) R^(D3) L_(C551) R^(D143) R^(D5) L_(C552) R^(D143)R^(D17) L_(C553) R^(D143) R^(D18) L_(C554) R^(D143) R^(D20) L_(C555)R^(D143) R^(D22) L_(C556) R^(D143) R^(D37) L_(C557) R^(D143) R^(D40)L_(C558) R^(D143) R^(D41) L_(C559) R^(D143) R^(D42) L_(C560) R^(D143)R^(D43) L_(C561) R^(D143) R^(D48) L_(C562) R^(D143) R^(D49) L_(C563)R^(D143) R^(D54) L_(C564) R^(D143) R^(D58) L_(C565) R^(D143) R^(D59)L_(C566) R^(D143) R^(D78) L_(C567) R^(D143) R^(D79) L_(C568) R^(D143)R^(D81) L_(C569) R^(D143) R^(D87) L_(C570) R^(D143) R^(D88) L_(C571)R^(D143) R^(D89) L_(C572) R^(D143) R^(D93) L_(C573) R^(D143) R^(D116)L_(C574) R^(D143) R^(D117) L_(C575) R^(D143) R^(D118) L_(C576) R^(D143)R^(D119) L_(C577) R^(D143) R^(D120) L_(C578) R^(D143) R^(D133) L_(C579)R^(D143) R^(D134) L_(C580) R^(D143) R^(D135) L_(C581) R^(D143) R^(D136)L_(C582) R^(D143) R^(D144) L_(C583) R^(D143) R^(D145) L_(C584) R^(D143)R^(D146) L_(C585) R^(D143) R^(D147) L_(C586) R^(D143) R^(D149) L_(C587)R^(D143) R^(D151) L_(C588) R^(D143) R^(D154) L_(C589) R^(D143) R^(D155)L_(C590) R^(D143) R^(D161) L_(C591) R^(D143) R^(D175) L_(C592) R^(D144)R^(D3) L_(C593) R^(D144) R^(D5) L_(C594) R^(D144) R^(D17) L_(C595)R^(D144) R^(D18) L_(C596) R^(D144) R^(D20) L_(C597) R^(D144) R^(D22)L_(C598) R^(D144) R^(D37) L_(C599) R^(D144) R^(D40) L_(C600) R^(D144)R^(D41) L_(C601) R^(D144) R^(D42) L_(C602) R^(D144) R^(D43) L_(C603)R^(D144) R^(D48) L_(C604) R^(D144) R^(D49) L_(C605) R^(D144) R^(D54)L_(C606) R^(D144) R^(D58) L_(C607) R^(D144) R^(D59) L_(C608) R^(D144)R^(D78) L_(C609) R^(D144) R^(D79) L_(C610) R^(D144) R^(D81) L_(C611)R^(D144) R^(D87) L_(C612) R^(D144) R^(D88) L_(C613) R^(D144) R^(D89)L_(C614) R^(D144) R^(D93) L_(C615) R^(D144) R^(D116) L_(C616) R^(D144)R^(D117) L_(C617) R^(D144) R^(D118) L_(C618) R^(D144) R^(D119) L_(C619)R^(D144) R^(D120) L_(C620) R^(D144) R^(D133) L_(C621) R^(D144) R^(D134)L_(C622) R^(D144) R^(D135) L_(C623) R^(D144) R^(D136) L_(C624) R^(D144)R^(D145) L_(C625) R^(D144) R^(D146) L_(C626) R^(D144) R^(D147) L_(C627)R^(D144) R^(D149) L_(C628) R^(D144) R^(D151) L_(C629) R^(D144) R^(D154)L_(C630) R^(D144) R^(D155) L_(C631) R^(D144) R^(D161) L_(C632) R^(D144)R^(D175) L_(C633) R^(D145) R^(D3) L_(C634) R^(D145) R^(D5) L_(C635)R^(D145) R^(D17) L_(C636) R^(D145) R^(D18) L_(C637) R^(D145) R^(D20)L_(C638) R^(D145) R^(D22) L_(C639) R^(D145) R^(D37) L_(C640) R^(D145)R^(D40) L_(C641) R^(D145) R^(D41) L_(C642) R^(D145) R^(D42) L_(C643)R^(D145) R^(D43) L_(C644) R^(D145) R^(D48) L_(C645) R^(D145) R^(D49)L_(C646) R^(D145) R^(D54) L_(C647) R^(D145) R^(D58) L_(C648) R^(D145)R^(D59) L_(C649) R^(D145) R^(D78) L_(C650) R^(D145) R^(D79) L_(C651)R^(D145) R^(D81) L_(C652) R^(D145) R^(D87) L_(C653) R^(D145) R^(D88)L_(C654) R^(D145) R^(D89) L_(C655) R^(D145) R^(D93) L_(C656) R^(D145)R^(D116) L_(C657) R^(D145) R^(D117) L_(C658) R^(D145) R^(D118) L_(C659)R^(D145) R^(D119) L_(C660) R^(D145) R^(D120) L_(C661) R^(D145) R^(D133)L_(C662) R^(D145) R^(D134) L_(C663) R^(D145) R^(D135) L_(C664) R^(D145)R^(D136) L_(C665) R^(D145) R^(D146) L_(C666) R^(D145) R^(D147) L_(C667)R^(D145) R^(D149) L_(C668) R^(D145) R^(D151) L_(C669) R^(D145) R^(D154)L_(C670) R^(D145) R^(D155) L_(C671) R^(D145) R^(D161) L_(C672) R^(D145)R^(D175) L_(C673) R^(D146) R^(D3) L_(C674) R^(D146) R^(D5) L_(C675)R^(D146) R^(D17) L_(C676) R^(D146) R^(D18) L_(C677) R^(D146) R^(D20)L_(C678) R^(D146) R^(D22) L_(C679) R^(D146) R^(D37) L_(C680) R^(D146)R^(D40) L_(C681) R^(D146) R^(D41) L_(C682) R^(D146) R^(D42) L_(C683)R^(D146) R^(D43) L_(C684) R^(D146) R^(D48) L_(C685) R^(D146) R^(D49)L_(C686) R^(D146) R^(D54) L_(C687) R^(D146) R^(D58) L_(C688) R^(D146)R^(D59) L_(C689) R^(D146) R^(D78) L_(C690) R^(D146) R^(D79) L_(C691)R^(D146) R^(D81) L_(C692) R^(D146) R^(D87) L_(C693) R^(D146) R^(D88)L_(C694) R^(D146) R^(D89) L_(C695) R^(D146) R^(D93) L_(C696) R^(D146)R^(D117) L_(C697) R^(D146) R^(D118) L_(C698) R^(D146) R^(D119) L_(C699)R^(D146) R^(D120) L_(C700) R^(D146) R^(D133) L_(C701) R^(D146) R^(D134)L_(C702) R^(D146) R^(D135) L_(C703) R^(D146) R^(D136) L_(C704) R^(D146)R^(D146) L_(C705) R^(D146) R^(D147) L_(C706) R^(D146) R^(D149) L_(C707)R^(D146) R^(D151) L_(C708) R^(D146) R^(D154) L_(C709) R^(D146) R^(D155)L_(C710) R^(D146) R^(D161) L_(C711) R^(D146) R^(D175) L_(C712) R^(D133)R^(D3) L_(C713) R^(D133) R^(D5) L_(C714) R^(D133) R^(D3) L_(C715)R^(D133) R^(D18) L_(C716) R^(D133) R^(D20) L_(C717) R^(D133) R^(D22)L_(C718) R^(D133) R^(D37) L_(C719) R^(D133) R^(D40) L_(C720) R^(D133)R^(D41) L_(C721) R^(D133) R^(D42) L_(C722) R^(D133) R^(D43) L_(C723)R^(D133) R^(D48) L_(C724) R^(D133) R^(D49) L_(C725) R^(D133) R^(D54)L_(C726) R^(D133) R^(D58) L_(C727) R^(D133) R^(D59) L_(C728) R^(D133)R^(D78) L_(C729) R^(D133) R^(D79) L_(C730) R^(D133) R^(D81) L_(C731)R^(D133) R^(D87) L_(C732) R^(D133) R^(D88) L_(C733) R^(D133) R^(D89)L_(C734) R^(D133) R^(D93) L_(C735) R^(D133) R^(D117) L_(C736) R^(D133)R^(D118) L_(C737) R^(D133) R^(D119) L_(C738) R^(D133) R^(D120) L_(C739)R^(D133) R^(D133) L_(C740) R^(D133) R^(D134) L_(C741) R^(D133) R^(D135)L_(C742) R^(D133) R^(D136) L_(C743) R^(D133) R^(D146) L_(C744) R^(D133)R^(D147) L_(C745) R^(D133) R^(D149) L_(C746) R^(D133) R^(D151) L_(C747)R^(D133) R^(D154) L_(C748) R^(D133) R^(D155) L_(C749) R^(D133) R^(D161)L_(C750) R^(D133) R^(D175) L_(C751) R^(D175) R^(D3) L_(C752) R^(D175)R^(D5) L_(C753) R^(D175) R^(D18) L_(C754) R^(D175) R^(D20) L_(C755)R^(D175) R^(D22) L_(C756) R^(D175) R^(D37) L_(C757) R^(D175) R^(D40)L_(C758) R^(D175) R^(D41) L_(C759) R^(D175) R^(D42) L_(C760) R^(D175)R^(D43) L_(C761) R^(D175) R^(D48) L_(C762) R^(D175) R^(D49) L_(C763)R^(D175) R^(D54) L_(C764) R^(D175) R^(D58) L_(C765) R^(D175) R^(D59)L_(C766) R^(D175) R^(D78) L_(C767) R^(D175) R^(D79) L_(C768) R^(D175)R^(D81) L_(C769) R^(D193) R^(D193) L_(C770) R^(D194) R^(D194) L_(C771)R^(D195) R^(D195) L_(C772) R^(D196) R^(D196) L_(C773) R^(D197) R^(D197)L_(C774) R^(D198) R^(D198) L_(C775) R^(D199) R^(D199) L_(C776) R^(D200)R^(D200) L_(C777) R^(D201) R^(D201) L_(C778) R^(D202) R^(D202) L_(C779)R^(D203) R^(D203) L_(C780) R^(D204) R^(D204) L_(C781) R^(D205) R^(D205)L_(C782) R^(D206) R^(D206) L_(C783) R^(D207) R^(D207) L_(C784) R^(D208)R^(D208) L_(C785) R^(D209) R^(D209) L_(C786) R^(D210) R^(D210) L_(C787)R^(D211) R^(D211) L_(C788) R^(D212) R^(D212) L_(C789) R^(D213) R^(D213)L_(C790) R^(D214) R^(D214) L_(C791) R^(D215) R^(D215) L_(C792) R^(D216)R^(D216) L_(C793) R^(D217) R^(D217) L_(C794) R^(D218) R^(D218) L_(C795)R^(D219) R^(D219) L_(C796) R^(D220) R^(D220) L_(C797) R^(D221) R^(D221)L_(C798) R^(D222) R^(D222) L_(C799) R^(D223) R^(D223) L_(C800) R^(D224)R^(D224) L_(C801) R^(D225) R^(D225) L_(C802) R^(D226) R^(D226) L_(C803)R^(D227) R^(D227) L_(C804) R^(D228) R^(D228) L_(C805) R^(D229) R^(D229)L_(C806) R^(D230) R^(D230) L_(C807) R^(D231) R^(D231) L_(C808) R^(D232)R^(D232) L_(C809) R^(D233) R^(D233) L_(C810) R^(D234) R^(D234) L_(C811)R^(D235) R^(D235) L_(C812) R^(D236) R^(D236) L_(C813) R^(D237) R^(D237)L_(C814) R^(D238) R^(D238) L_(C815) R^(D239) R^(D239) L_(C816) R^(D240)R^(D240) L_(C817) R^(D241) R^(D241) L_(C818) R^(D242) R^(D242) L_(C819)R^(D243) R^(D243) L_(C820) R^(D244) R^(D244) L_(C821) R^(D245) R^(D245)L_(C822) R^(D246) R^(D246) L_(C823) R^(D17) R^(D193) L_(C824) R^(D17)R^(D194) L_(C825) R^(D17) R^(D195) L_(C826) R^(D17) R^(D196) L_(C827)R^(D17) R^(D197) L_(C828) R^(D17) R^(D198) L_(C829) R^(D17) R^(D199)L_(C830) R^(D17) R^(D200) L_(C831) R^(D17) R^(D201) L_(C832) R^(D17)R^(D202) L_(C833) R^(D17) R^(D203) L_(C834) R^(D17) R^(D204) L_(C835)R^(D17) R^(D205) L_(C836) R^(D17) R^(D206) L_(C837) R^(D17) R^(D207)L_(C838) R^(D17) R^(D208) L_(C839) R^(D17) R^(D209) L_(C840) R^(D17)R^(D210) L_(C841) R^(D17) R^(D211) L_(C842) R^(D17) R^(D212) L_(C843)R^(D17) R^(D213) L_(C844) R^(D17) R^(D214) L_(C845) R^(D17) R^(D215)L_(C846) R^(D17) R^(D216) L_(C847) R^(D17) R^(D217) L_(C848) R^(D17)R^(D218) L_(C849) R^(D17) R^(D219) L_(C850) R^(D17) R^(D220) L_(C851)R^(D17) R^(D221) L_(C852) R^(D17) R^(D222) L_(C853) R^(D17) R^(D223)L_(C854) R^(D17) R^(D224) L_(C855) R^(D17) R^(D225) L_(C856) R^(D17)R^(D226) L_(C857) R^(D17) R^(D227) L_(C858) R^(D17) R^(D228) L_(C859)R^(D17) R^(D229) L_(C860) R^(D17) R^(D230) L_(C861) R^(D17) R^(D231)L_(C862) R^(D17) R^(D232) L_(C863) R^(D17) R^(D233) L_(C864) R^(D17)R^(D234) L_(C865) R^(D17) R^(D235) L_(C866) R^(D17) R^(D236) L_(C867)R^(D17) R^(D237) L_(C868) R^(D17) R^(D238) L_(C869) R^(D17) R^(D239)L_(C870) R^(D17) R^(D240) L_(C871) R^(D17) R^(D241) L_(C872) R^(D17)R^(D242) L_(C873) R^(D17) R^(D243) L_(C874) R^(D17) R^(D244) L_(C875)R^(D17) R^(D245) L_(C876) R^(D17) R^(D246) L_(C877) R^(D1) R^(D193)L_(C878) R^(D1) R^(D194) L_(C879) R^(D1) R^(D195) L_(C880) R^(D1)R^(D196) L_(C881) R^(D1) R^(D197) L_(C882) R^(D1) R^(D198) L_(C883)R^(D1) R^(D199) L_(C884) R^(D1) R^(D200) L_(C885) R^(D1) R^(D201)L_(C886) R^(D1) R^(D202) L_(C887) R^(D1) R^(D203) L_(C888) R^(D1)R^(D204) L_(C889) R^(D1) R^(D205) L_(C890) R^(D1) R^(D206) L_(C891)R^(D1) R^(D207) L_(C892) R^(D1) R^(D208) L_(C893) R^(D1) R^(D209)L_(C894) R^(D1) R^(D210) L_(C895) R^(D1) R^(D211) L_(C896) R^(D1)R^(D212) L_(C897) R^(D1) R^(D213) L_(C898) R^(D1) R^(D214) L_(C899)R^(D1) R^(D215) L_(C900) R^(D1) R^(D216) L_(C901) R^(D1) R^(D217)L_(C902) R^(D1) R^(D218) L_(C903) R^(D1) R^(D219) L_(C904) R^(D1)R^(D220) L_(C905) R^(D1) R^(D221) L_(C906) R^(D1) R^(D222) L_(C907)R^(D1) R^(D223) L_(C908) R^(D1) R^(D224) L_(C909) R^(D1) R^(D225)L_(C910) R^(D1) R^(D226) L_(C911) R^(D1) R^(D227) L_(C912) R^(D1)R^(D228) L_(C913) R^(D1) R^(D229) L_(C914) R^(D1) R^(D230) L_(C915)R^(D1) R^(D231) L_(C916) R^(D1) R^(D232) L_(C917) R^(D1) R^(D233)L_(C918) R^(D1) R^(D234) L_(C919) R^(D1) R^(D235) L_(C920) R^(D1)R^(D236) L_(C921) R^(D1) R^(D237) L_(C922) R^(D1) R^(D238) L_(C923)R^(D1) R^(D239) L_(C924) R^(D1) R^(D240) L_(C925) R^(D1) R^(D241)L_(C926) R^(D1) R^(D242) L_(C927) R^(D1) R^(D243) L_(C928) R^(D1)R^(D244) L_(C929) R^(D1) R^(D245) L_(C930) R^(D1) R^(D246) L_(C931)R^(D50) R^(D193) L_(C932) R^(D50) R^(D194) L_(C933) R^(D50) R^(D195)L_(C934) R^(D50) R^(D196) L_(C935) R^(D50) R^(D197) L_(C936) R^(D50)R^(D198) L_(C937) R^(D50) R^(D199) L_(C938) R^(D50) R^(D200) L_(C939)R^(D50) R^(D201) L_(C940) R^(D50) R^(D202) L_(C941) R^(D50) R^(D203)L_(C942) R^(D50) R^(D204) L_(C943) R^(D50) R^(D205) L_(C944) R^(D50)R^(D206) L_(C945) R^(D50) R^(D207) L_(C946) R^(D50) R^(D208) L_(C947)R^(D50) R^(D209) L_(C948) R^(D50) R^(D210) L_(C949) R^(D50) R^(D211)L_(C950) R^(D50) R^(D212) L_(C951) R^(D50) R^(D213) L_(C952) R^(D50)R^(D214) L_(C953) R^(D50) R^(D215) L_(C954) R^(D50) R^(D216) L_(C955)R^(D50) R^(D217) L_(C956) R^(D50) R^(D218) L_(C957) R^(D50) R^(D219)L_(C958) R^(D50) R^(D220) L_(C959) R^(D50) R^(D221) L_(C960) R^(D50)R^(D222) L_(C961) R^(D50) R^(D223) L_(C962) R^(D50) R^(D224) L_(C963)R^(D50) R^(D225) L_(C964) R^(D50) R^(D226) L_(C965) R^(D50) R^(D227)L_(C966) R^(D50) R^(D228) L_(C967) R^(D50) R^(D229) L_(C968) R^(D50)R^(D230) L_(C969) R^(D50) R^(D231) L_(C970) R^(D50) R^(D232) L_(C971)R^(D50) R^(D233) L_(C972) R^(D50) R^(D234) L_(C973) R^(D50) R^(D235)L_(C974) R^(D50) R^(D236) L_(C975) R^(D50) R^(D237) L_(C976) R^(D50)R^(D238) L_(C977) R^(D50) R^(D239) L_(C978) R^(D50) R^(D240) L_(C979)R^(D50) R^(D241) L_(C980) R^(D50) R^(D242) L_(C981) R^(D50) R^(D243)L_(C982) R^(D50) R^(D244) L_(C983) R^(D50) R^(D245) L_(C984) R^(D50)R^(D246) L_(C985) R^(D4) R^(D193) L_(C986) R^(D4) R^(D194) L_(C987)R^(D4) R^(D195) L_(C988) R^(D4) R^(D196) L_(C989) R^(D4) R^(D197)L_(C990) R^(D4) R^(D198) L_(C991) R^(D4) R^(D199) L_(C992) R^(D4)R^(D200) L_(C993) R^(D4) R^(D201) L_(C994) R^(D4) R^(D202) L_(C995)R^(D4) R^(D203) L_(C996) R^(D4) R^(D204) L_(C997) R^(D4) R^(D205)L_(C998) R^(D4) R^(D206) L_(C999) R^(D4) R^(D207) L_(C1000) R^(D4)R^(D208) L_(C1001) R^(D4) R^(D209) L_(C1002) R^(D4) R^(D210) L_(C1003)R^(D4) R^(D211) L_(C1004) R^(D4) R^(D212) L_(C1005) R^(D4) R^(D213)L_(C1006) R^(D4) R^(D214) L_(C1007) R^(D4) R^(D215) L_(C1008) R^(D4)R^(D216) L_(C1009) R^(D4) R^(D217) L_(C1010) R^(D4) R^(D218) L_(C1011)R^(D4) R^(D219) L_(C1012) R^(D4) R^(D220) L_(C1013) R^(D4) R^(D221)L_(C1014) R^(D4) R^(D222) L_(C1015) R^(D4) R^(D223) L_(C1016) R^(D4)R^(D224) L_(C1017) R^(D4) R^(D225) L_(C1018) R^(D4) R^(D226) L_(C1019)R^(D4) R^(D227) L_(C1020) R^(D4) R^(D228) L_(C1021) R^(D4) R^(D229)L_(C1022) R^(D4) R^(D230) L_(C1023) R^(D4) R^(D231) L_(C1024) R^(D4)R^(D232) L_(C1025) R^(D4) R^(D233) L_(C1026) R^(D4) R^(D234) L_(C1027)R^(D4) R^(D235) L_(C1028) R^(D4) R^(D236) L_(C1029) R^(D4) R^(D237)L_(C1030) R^(D4) R^(D238) L_(C1031) R^(D4) R^(D239) L_(C1032) R^(D4)R^(D240) L_(C1033) R^(D4) R^(D241) L_(C1034) R^(D4) R^(D242) L_(C1035)R^(D4) R^(D243) L_(C1036) R^(D4) R^(D244) L_(C1037) R^(D4) R^(D245)L_(C1038) R^(D4) R^(D246) L_(C1039) R^(D145) R^(D193) L_(C1040) R^(D145)R^(D194) L_(C1041) R^(D145) R^(D195) L_(C1042) R^(D145) R^(D196)L_(C1043) R^(D145) R^(D197) L_(C1044) R^(D145) R^(D198) L_(C1045)R^(D145) R^(D199) L_(C1046) R^(D145) R^(D200) L_(C1047) R^(D145)R^(D201) L_(C1048) R^(D145) R^(D202) L_(C1049) R^(D145) R^(D203)L_(C1050) R^(D145) R^(D204) L_(C1051) R^(D145) R^(D205) L_(C1052)R^(D145) R^(D206) L_(C1053) R^(D145) R^(D207) L_(C1054) R^(D145)R^(D208) L_(C1055) R^(D145) R^(D209) L_(C1056) R^(D145) R^(D210)L_(C1057) R^(D145) R^(D211) L_(C1058) R^(D145) R^(D212) L_(C1059)R^(D145) R^(D213) L_(C1060) R^(D145) R^(D214) L_(C1061) R^(D145)R^(D215) L_(C1062) R^(D145) R^(D216) L_(C1063) R^(D145) R^(D217)L_(C1064) R^(D145) R^(D218) L_(C1065) R^(D145) R^(D219) L_(C1066)R^(D145) R^(D220) L_(C1067) R^(D145) R^(D221) L_(C1068) R^(D145)R^(D222) L_(C1069) R^(D145) R^(D223) L_(C1070) R^(D145) R^(D224)L_(C1071) R^(D145) R^(D225) L_(C1072) R^(D145) R^(D226) L_(C1073)R^(D145) R^(D227) L_(C1074) R^(D145) R^(D228) L_(C1075) R^(D145)R^(D229) L_(C1076) R^(D145) R^(D230) L_(C1077) R^(D145) R^(D231)L_(C1078) R^(D145) R^(D232) L_(C1079) R^(D145) R^(D233) L_(C1080)R^(D145) R^(D234) L_(C1081) R^(D145) R^(D235) L_(C1082) R^(D145)R^(D236) L_(C1083) R^(D145) R^(D237) L_(C1084) R^(D145) R^(D238)L_(C1085) R^(D145) R^(D239) L_(C1086) R^(D145) R^(D240) L_(C1087)R^(D145) R^(D241) L_(C1088) R^(D145) R^(D242) L_(C1089) R^(D145)R^(D243) L_(C1090) R^(D145) R^(D244) L_(C1091) R^(D145) R^(D245)L_(C1092) R^(D145) R^(D246) L_(C1093) R^(D9) R^(D193) L_(C1094) R^(D9)R^(D194) L_(C1095) R^(D9) R^(D195) L_(C1096) R^(D9) R^(D196) L_(C1097)R^(D9) R^(D197) L_(C1098) R^(D9) R^(D198) L_(C1099) R^(D9) R^(D199)L_(C1100) R^(D9) R^(D200) L_(C1101) R^(D9) R^(D201) L_(C1102) R^(D9)R^(D202) L_(C1103) R^(D9) R^(D203) L_(C1104) R^(D9) R^(D204) L_(C1105)R^(D9) R^(D205) L_(C1106) R^(D9) R^(D206) L_(C1107) R^(D9) R^(D207)L_(C1108) R^(D9) R^(D208) L_(C1109) R^(D9) R^(D209) L_(C1110) R^(D9)R^(D210) L_(C1111) R^(D9) R^(D211) L_(C1112) R^(D9) R^(D212) L_(C1113)R^(D9) R^(D213) L_(C1114) R^(D9) R^(D214) L_(C1115) R^(D9) R^(D215)L_(C1116) R^(D9) R^(D216) L_(C1117) R^(D9) R^(D217) L_(C1118) R^(D9)R^(D218) L_(C1119) R^(D9) R^(D219) L_(C1120) R^(D9) R^(D220) L_(C1121)R^(D9) R^(D221) L_(C1122) R^(D9) R^(D222) L_(C1123) R^(D9) R^(D223)L_(C1124) R^(D9) R^(D224) L_(C1125) R^(D9) R^(D225) L_(C1126) R^(D9)R^(D226) L_(C1127) R^(D9) R^(D227) L_(C1128) R^(D9) R^(D228) L_(C1129)R^(D9) R^(D229) L_(C1130) R^(D9) R^(D230) L_(C1131) R^(D9) R^(D231)L_(C1132) R^(D9) R^(D232) L_(C1133) R^(D9) R^(D233) L_(C1134) R^(D9)R^(D234) L_(C1135) R^(D9) R^(D235) L_(C1136) R^(D9) R^(D236) L_(C1137)R^(D9) R^(D237) L_(C1138) R^(D9) R^(D238) L_(C1139) R^(D9) R^(D239)L_(C1140) R^(D9) R^(D240) L_(C1141) R^(D9) R^(D241) L_(C1142) R^(D9)R^(D242) L_(C1143) R^(D9) R^(D243) L_(C1144) R^(D9) R^(D244) L_(C1145)R^(D9) R^(D245) L_(C1146) R^(D9) R^(D246) L_(C1147) R^(D168) R^(D193)L_(C1148) R^(D168) R^(D194) L_(C1149) R^(D168) R^(D195) L_(C1150)R^(D168) R^(D196) L_(C1151) R^(D168) R^(D197) L_(C1152) R^(D168)R^(D198) L_(C1153) R^(D168) R^(D199) L_(C1154) R^(D168) R^(D200)L_(C1155) R^(D168) R^(D201) L_(C1156) R^(D168) R^(D202) L_(C1157)R^(D168) R^(D203) L_(C1158) R^(D168) R^(D204) L_(C1159) R^(D168)R^(D205) L_(C1160) R^(D168) R^(D206) L_(C1161) R^(D168) R^(D207)L_(C1162) R^(D168) R^(D208) L_(C1163) R^(D168) R^(D209) L_(C1164)R^(D168) R^(D210) L_(C1165) R^(D168) R^(D211) L_(C1166) R^(D168)R^(D212) L_(C1167) R^(D168) R^(D213) L_(C1168) R^(D168) R^(D214)L_(C1169) R^(D168) R^(D215) L_(C1170) R^(D168) R^(D216) L_(C1171)R^(D168) R^(D217) L_(C1172) R^(D168) R^(D218) L_(C1173) R^(D168)R^(D219) L_(C1174) R^(D168) R^(D220) L_(C1175) R^(D168) R^(D221)L_(C1176) R^(D168) R^(D222) L_(C1177) R^(D168) R^(D223) L_(C1178)R^(D168) R^(D224) L_(C1179) R^(D168) R^(D225) L_(C1180) R^(D168)R^(D226) L_(C1181) R^(D168) R^(D227) L_(C1182) R^(D168) R^(D228)L_(C1183) R^(D168) R^(D229) L_(C1184) R^(D168) R^(D230) L_(C1185)R^(D168) R^(D231) L_(C1186) R^(D168) R^(D232) L_(C1187) R^(D168)R^(D233) L_(C1188) R^(D168) R^(D234) L_(C1189) R^(D168) R^(D235)L_(C1190) R^(D168) R^(D236) L_(C1191) R^(D168) R^(D237) L_(C1192)R^(D168) R^(D238) L_(C1193) R^(D168) R^(D239) L_(C1194) R^(D168)R^(D240) L_(C1195) R^(D168) R^(D241) L_(C1196) R^(D168) R^(D242)L_(C1197) R^(D168) R^(D243) L_(C1198) R^(D168) R^(D244) L_(C1199)R^(D168) R^(D245) L_(C1200) R^(D168) R^(D246) L_(C1201) R^(D10) R^(D193)L_(C1202) R^(D10) R^(D194) L_(C1203) R^(D10) R^(D195) L_(C1204) R^(D10)R^(D196) L_(C1205) R^(D10) R^(D197) L_(C1206) R^(D10) R^(D198) L_(C1207)R^(D10) R^(D199) L_(C1208) R^(D10) R^(D200) L_(C1209) R^(D10) R^(D201)L_(C1210) R^(D10) R^(D202) L_(C1211) R^(D10) R^(D203) L_(C1212) R^(D10)R^(D204) L_(C1213) R^(D10) R^(D205) L_(C1214) R^(D10) R^(D206) L_(C1215)R^(D10) R^(D207) L_(C1216) R^(D10) R^(D208) L_(C1217) R^(D10) R^(D209)L_(C1218) R^(D10) R^(D210) L_(C1219) R^(D10) R^(D211) L_(C1220) R^(D10)R^(D212) L_(C1221) R^(D10) R^(D213) L_(C1222) R^(D10) R^(D214) L_(C1223)R^(D10) R^(D215) L_(C1224) R^(D10) R^(D216) L_(C1225) R^(D10) R^(D217)L_(C1226) R^(D10) R^(D218) L_(C1227) R^(D10) R^(D219) L_(C1228) R^(D10)R^(D220) L_(C1229) R^(D10) R^(D221) L_(C1230) R^(D10) R^(D222) L_(C1231)R^(D10) R^(D223) L_(C1232) R^(D10) R^(D224) L_(C1233) R^(D10) R^(D225)L_(C1234) R^(D10) R^(D226) L_(C1235) R^(D10) R^(D227) L_(C1236) R^(D10)R^(D228) L_(C1237) R^(D10) R^(D229) L_(C1238) R^(D10) R^(D230) L_(C1239)R^(D10) R^(D231) L_(C1240) R^(D10) R^(D232) L_(C1241) R^(D10) R^(D233)L_(C1242) R^(D10) R^(D234) L_(C1243) R^(D10) R^(D235) L_(C1244) R^(D10)R^(D236) L_(C1245) R^(D10) R^(D237) L_(C1246) R^(D10) R^(D238) L_(C1247)R^(D10) R^(D239) L_(C1248) R^(D10) R^(D240) L_(C1249) R^(D10) R^(D241)L_(C1250) R^(D10) R^(D242) L_(C1251) R^(D10) R^(D243) L_(C1252) R^(D10)R^(D244) L_(C1253) R^(D10) R^(D245) L_(C1254) R^(D10) R^(D246) L_(C1255)R^(D55) R^(D193) L_(C1256) R^(D55) R^(D194) L_(C1257) R^(D55) R^(D195)L_(C1258) R^(D55) R^(D196) L_(C1259) R^(D55) R^(D197) L_(C1260) R^(D55)R^(D198) L_(C1261) R^(D55) R^(D199) L_(C1262) R^(D55) R^(D200) L_(C1263)R^(D55) R^(D201) L_(C1264) R^(D55) R^(D202) L_(C1265) R^(D55) R^(D203)L_(C1266) R^(D55) R^(D204) L_(C1267) R^(D55) R^(D205) L_(C1268) R^(D55)R^(D206) L_(C1269) R^(D55) R^(D207) L_(C1270) R^(D55) R^(D208) L_(C1271)R^(D55) R^(D209) L_(C1272) R^(D55) R^(D210) L_(C1273) R^(D55) R^(D211)L_(C1274) R^(D55) R^(D212) L_(C1275) R^(D55) R^(D213) L_(C1276) R^(D55)R^(D214) L_(C1277) R^(D55) R^(D215) L_(C1278) R^(D55) R^(D216) L_(C1279)R^(D55) R^(D217) L_(C1280) R^(D55) R^(D218) L_(C1281) R^(D55) R^(D219)L_(C1282) R^(D55) R^(D220) L_(C1283) R^(D55) R^(D221) L_(C1284) R^(D55)R^(D222) L_(C1285) R^(D55) R^(D223) L_(C1286) R^(D55) R^(D224) L_(C1287)R^(D55) R^(D225) L_(C1288) R^(D55) R^(D226) L_(C1289) R^(D55) R^(D227)L_(C1290) R^(D55) R^(D228) L_(C1291) R^(D55) R^(D229) L_(C1292) R^(D55)R^(D230) L_(C1293) R^(D55) R^(D231) L_(C1294) R^(D55) R^(D232) L_(C1295)R^(D55) R^(D233) L_(C1296) R^(D55) R^(D234) L_(C1297) R^(D55) R^(D235)L_(C1298) R^(D55) R^(D236) L_(C1299) R^(D55) R^(D237) L_(C1300) R^(D55)R^(D238) L_(C1301) R^(D55) R^(D239) L_(C1302) R^(D55) R^(D240) L_(C1303)R^(D55) R^(D241) L_(C1304) R^(D55) R^(D242) L_(C1305) R^(D55) R^(D243)L_(C1306) R^(D55) R^(D244) L_(C1307) R^(D55) R^(D245) L_(C1308) R^(D55)R^(D246) L_(C1309) R^(D37) R^(D193) L_(C1310) R^(D37) R^(D194) L_(C1311)R^(D37) R^(D195) L_(C1312) R^(D37) R^(D196) L_(C1313) R^(D37) R^(D197)L_(C1314) R^(D37) R^(D198) L_(C1315) R^(D37) R^(D199) L_(C1316) R^(D37)R^(D200) L_(C1317) R^(D37) R^(D201) L_(C1318) R^(D37) R^(D202) L_(C1319)R^(D37) R^(D203) L_(C1320) R^(D37) R^(D204) L_(C1321) R^(D37) R^(D205)L_(C1322) R^(D37) R^(D206) L_(C1323) R^(D37) R^(D207) L_(C1324) R^(D37)R^(D208) L_(C1325) R^(D37) R^(D209) L_(C1326) R^(D37) R^(D210) L_(C1327)R^(D37) R^(D211) L_(C1328) R^(D37) R^(D212) L_(C1329) R^(D37) R^(D213)L_(C1330) R^(D37) R^(D214) L_(C1331) R^(D37) R^(D215) L_(C1332) R^(D37)R^(D216) L_(C1333) R^(D37) R^(D217) L_(C1334) R^(D37) R^(D218) L_(C1335)R^(D37) R^(D219) L_(C1336) R^(D37) R^(D220) L_(C1337) R^(D37) R^(D221)L_(C1338) R^(D37) R^(D222) L_(C1339) R^(D37) R^(D223) L_(C1340) R^(D37)R^(D224) L_(C1341) R^(D37) R^(D225) L_(C1342) R^(D37) R^(D226) L_(C1343)R^(D37) R^(D227) L_(C1344) R^(D37) R^(D228) L_(C1345) R^(D37) R^(D229)L_(C1346) R^(D37) R^(D230) L_(C1347) R^(D37) R^(D231) L_(C1348) R^(D37)R^(D232) L_(C1349) R^(D37) R^(D233) L_(C1350) R^(D37) R^(D234) L_(C1351)R^(D37) R^(D235) L_(C1352) R^(D37) R^(D236) L_(C1353) R^(D37) R^(D237)L_(C1354) R^(D37) R^(D238) L_(C1355) R^(D37) R^(D239) L_(C1356) R^(D37)R^(D240) L_(C1357) R^(D37) R^(D241) L_(C1358) R^(D37) R^(D242) L_(C1359)R^(D37) R^(D243) L_(C1360) R^(D37) R^(D244) L_(C1361) R^(D37) R^(D245)L_(C1362) R^(D37) R^(D246) L_(C1363) R^(D143) R^(D193) L_(C1364)R^(D143) R^(D194) L_(C1365) R^(D143) R^(D195) L_(C1366) R^(D143)R^(D196) L_(C1367) R^(D143) R^(D197) L_(C1368) R^(D143) R^(D198)L_(C1369) R^(D143) R^(D199) L_(C1370) R^(D143) R^(D200) L_(C1371)R^(D143) R^(D201) L_(C1372) R^(D143) R^(D202) L_(C1373) R^(D143)R^(D203) L_(C1374) R^(D143) R^(D204) L_(C1375) R^(D143) R^(D205)L_(C1376) R^(D143) R^(D206) L_(C1377) R^(D143) R^(D207) L_(C1378)R^(D143) R^(D208) L_(C1379) R^(D143) R^(D209) L_(C1380) R^(D143)R^(D210) L_(C1381) R^(D143) R^(D211) L_(C1382) R^(D143) R^(D212)L_(C1383) R^(D143) R^(D213) L_(C1384) R^(D143) R^(D214) L_(C1385)R^(D143) R^(D215) L_(C1386) R^(D143) R^(D216) L_(C1387) R^(D143)R^(D217) L_(C1388) R^(D143) R^(D218) L_(C1389) R^(D143) R^(D219)L_(C1390) R^(D143) R^(D220) L_(C1391) R^(D143) R^(D221) L_(C1392)R^(D143) R^(D222) L_(C1393) R^(D143) R^(D223) L_(C1394) R^(D143)R^(D224) L_(C1395) R^(D143) R^(D225) L_(C1396) R^(D143) R^(D226)L_(C1397) R^(D143) R^(D227) L_(C1398) R^(D143) R^(D228) L_(C1399)R^(D143) R^(D229) L_(C1400) R^(D143) R^(D230) L_(C1401) R^(D143)R^(D231) L_(C1402) R^(D143) R^(D232) L_(C1403) R^(D143) R^(D233)L_(C1404) R^(D143) R^(D234) L_(C1405) R^(D143) R^(D235) L_(C1406)R^(D143) R^(D236) L_(C1407) R^(D143) R^(D237) L_(C1408) R^(D143)R^(D238) L_(C1409) R^(D143) R^(D239) L_(C1410) R^(D143) R^(D240)L_(C1411) R^(D143) R^(D241) L_(C1412) R^(D143) R^(D242) L_(C1413)R^(D143) R^(D243) L_(C1414) R^(D143) R^(D244) L_(C1415) R^(D143)R^(D245) L_(C1416) R^(D143) R^(D246)wherein R^(D1) to R^(D246) have the structures in the following LIST 8:

In some embodiments, the compound has the formula Ir(L_(A))(L_(Bk))₂ orIr(L_(A))₂(L_(Bk)), wherein the compound is selected from the groupconsisting of only those compounds having one of the followingstructures for the L_(Bk) ligand: L_(B1), L_(B2), L_(B18), L_(B28),L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128),L_(B130), L_(B32), L_(B134), L_(B136), L_(B138), L_(B140), L_(B142),L_(B144), L_(B156), L_(B58), L_(B160), L_(B162), L_(B164), L_(B168),L_(B172), L_(B175), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218),L_(B220), L_(B222), L_(B231), L_(B233), L_(B235), L_(B237), L_(B240),L_(B242), L_(B244), L_(B246), L_(B248), L_(B250), L_(B252), L_(B254),L_(B256), L_(B258), L_(B260), L_(B262), L_(B263), L_(B264), L_(B265),L_(B266), L_(B267), L_(B268), L_(B269), and L_(B270).

In some embodiments, the compound has the formula Ir(L_(A))(L_(Bk))₂ orIr(L_(A))₂(L_(Bk)), wherein the compound is selected from the groupconsisting of only those compounds having one of the followingstructures for the L_(Bk) ligand: L_(B1), L_(B2), L_(B18), L_(B28),L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128),L_(B132), L_(B136), L_(B138), L_(B142), L_(B156), L_(B162), L_(B204),L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B231), L_(B233),L_(B37), L_(B265), L_(B266), L_(B267), L_(B268), L_(B269), and L_(B270).

In some embodiments, L_(Cj-I) and L_(Cj-II) are each independentlyselected from only those structures in their corresponding group whosecorresponding R²⁰¹ and R²⁰² are one of the following structures: R^(D1),R^(D3), R^(D4), R^(D5), R^(D9), R^(D10), R^(D17), R^(D18), R^(D20),R^(D22), R^(D37), R^(D40), R^(D41), R^(D42), R^(D43), R^(D48), R^(D49),R^(D50), R^(D54), R^(D55), R^(D58), R^(D59), R^(D78), R^(D79), R^(D81),R^(D87), R^(D88), R^(D89), R^(D93), R^(D116), R^(D117), R^(D118),R^(D119), R^(D120), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143),R^(D144), R^(D145), R^(D146), R^(D147), R^(D149), R^(D151), R^(D154),R^(D155), R^(D156), R^(D175), R^(D1190), R^(D193), R^(D200), R^(D201),R^(D206), R^(D210), R^(D214), R^(D215), R^(D216), R^(D218), R^(D219),R^(D220), R^(D227), R^(D237), R^(D241), R^(D242), R^(D245), andR^(D246).

In some embodiments, L_(Cj-I) and L_(Cj-II) are each independentlyselected from only those structures in their corresponding group whosecorresponding R²⁰¹ and R²² are one of selected from the followingstructures R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D10), R^(D17),R^(D22), R^(D43), R^(D50), R^(D78), R^(D116), R^(D118), R^(D133),R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146),R^(D149), R^(D151), R^(D154), R^(D155), R^(D190), R^(D193), R^(D200),R^(D201), R^(D206), R^(D210), R^(D214), R^(D215), R^(D216), R^(D218),R^(D219), R^(D220), R^(D227), R^(D237), R^(D241), R^(D242), R^(D245),and R^(D246).

In some embodiments, the compound has the formula Ir(L_(A))₂(L_(Cj-I)),and the compound is selected from the group consisting of only thosecompounds having one of the structures of the following LIST 9 for theL_(Cj-I) ligand:

In some embodiments, the compound is selected from the group consistingof the structures of the following LIST 10:

In some embodiments, the compound has a structure of Formula II,

In the structure of Formula II:

M¹ is Pd or Pt;

rings E and F are each independently a 5-membered or 6-memberedcarbocyclic or heterocyclic ring;

Z and Z′ are each independently C or N;

K¹ and K² are each independently selected from the group consisting of adirect bond, O, and S, wherein at least one of K¹ and K² is a directbond;

L¹ is an organic linker;

L², L³ and L⁴ are each independently selected from the group consistingof a single bond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′,wherein at least one of L², L³ and L⁴ is present;

X³ and X⁴ are each independently C or N;

R^(E) and R^(F) each independently represents zero, mono, or up to amaximum allowed substitution to its associated ring;

each of R′, R″, R^(E), and R^(F) is independently a hydrogen or asubstituent selected from the group consisting of the preferred generalsubstituents defined herein; and

any two adjacent R^(A), R^(B), R, R′, R″ R^(E), and R^(F) can be joinedor fused together to form a ring.

In some embodiments of Formula II, ring E and ring F are both 6-memberedaromatic rings.

In some embodiments of Formula II, ring F is a 5-membered or 6-memberedheteroaromatic ring.

In some embodiments of Formula II, L¹ is O or CR′R″.

In some embodiments of Formula II, Z′ is N and Z is C. In someembodiments of Formula II, Z′ is C and Z is N.

In some embodiments of Formula II, L² is a direct bond. In someembodiments of Formula II, L² is NR′.

In some embodiments of Formula II, K¹ and K² are both direct bonds.

In some embodiments of Formula II, X³ and X⁴ are both C.

In some embodiments, the compound is selected from the group consistingof the structures in the following LIST 11:

wherein: L^(1a) is selected from the group of —CR═N—, —CR′R″CR′R″—,—NR′BR—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—,—CR′═CR″CR₂—, —C(═CR—)—, and —C(═N—)—; L^(1b) is selected from the groupof —CR═N—, —CR₂—, —CR═CR′—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—,—CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR₂—, —C(═CR—)—, and—C(═N—)—; R^(Y) are each selected from the group consisting of alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, andcombinations thereof; each R^(G) is independently a hydrogen or asubstituent selected from the group consisting of the preferred generalsubstituents defined herein; and any two R^(A), R^(B), R^(E), R^(F),R^(G), R^(Y), R, R′ and R″ can be joined together to form a ring.

In some embodiments, the compound is selected from the group consistingof the structures in the following LIST 12:

C. The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED devicecomprising a first organic layer that contains a compound as disclosedin the above compounds section of the present disclosure.

In some embodiments, the OLED comprises an anode, a cathode, and a firstorganic layer disposed between the anode and the cathode. The firstorganic layer can comprise a compound comprising a ligand L_(A) ofFormula I described herein.

In some embodiments, the organic layer may be an emissive layer and thecompound as described herein may be an emissive dopant or a non-emissivedopant.

In some embodiments, the organic layer may further comprise a host,wherein the host comprises a triphenylene containing benzo-fusedthiophene or benzo-fused furan, wherein any substituent in the host isan unfused substituent independently selected from the group consistingof C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂),CH═CH—C_(n)H_(2n+1), C≡CC_(n)H_(2n+1), Ar₁, Ar₁—Ar₂, C_(n)H_(2n+1)—Ar₁,or no substitution, wherein n is from 1 to 10; and wherein Ar₁ and Ar₂are independently selected from the group consisting of benzene,biphenyl, naphthalene, triphenylene, carbazole, and heteroaromaticanalogs thereof.

In some embodiments, the organic layer may further comprise a host,wherein host comprises at least one chemical group selected from thegroup consisting of triphenylene, carbazole, indolocarbazole,dibenzothiophene, dibenzofuran, dibenzoselenophene,5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene,aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene,aza-dibenzofuran, aza-dibenzoselenophene, andaza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

In some embodiments, the host may be selected from the HOST Groupconsisting of:

and combinations thereof.

In some embodiments, the organic layer may further comprise a host,wherein the host comprises a metal complex.

In some embodiments, the compound as described herein may be asensitizer; wherein the device may further comprise an acceptor; andwherein the acceptor may be selected from the group consisting offluorescent emitter, delayed fluorescence emitter, and combinationthereof.

In yet another aspect, the OLED of the present disclosure may alsocomprise an emissive region containing a compound as disclosed in theabove compounds section of the present disclosure.

In some embodiments, the emissive region can comprise a compoundcomprising a ligand L_(A) of Formula I described herein.

In some embodiments, at least one of the anode, the cathode, or anewlayer disposed over the organic emissive layer functions as anenhancement layer. The enhancement layer comprises a plasmonic materialexhibiting surface plasmon resonance that non-radiatively couples to theemitter material and transfers excited state energy from the emittermaterial to non-radiative mode of surface plasmon polariton. Theenhancement layer is provided no more than a threshold distance awayfrom the organic emissive layer, wherein the emitter material has atotal non-radiative decay rate constant and a total radiative decay rateconstant due to the presence of the enhancement layer and the thresholddistance is where the total non-radiative decay rate constant is equalto the total radiative decay rate constant. In some embodiments, theOLED further comprises an outcoupling layer. In some embodiments, theoutcoupling layer is disposed over the enhancement layer on the oppositeside of the organic emissive layer. In some embodiments, the outcouplinglayer is disposed on opposite side of the emissive layer from theenhancement layer but still outcouples energy from the surface plasmonmode of the enhancement layer. The outcoupling layer scatters the energyfrom the surface plasmon polaritons. In some embodiments this energy isscattered as photons to free space. In other embodiments, the energy isscattered from the surface plasmon mode into other modes of the devicesuch as but not limited to the organic waveguide mode, the substratemode, or another waveguiding mode. If energy is scattered to thenon-free space mode of the OLED other outcoupling schemes could beincorporated to extract that energy to free space. In some embodiments,one or more intervening layer can be disposed between the enhancementlayer and the outcoupling layer. The examples for interventing layer(s)can be dielectric materials, including organic, inorganic, perovskites,oxides, and may include stacks and/or mixtures of these materials.

The enhancement layer modifies the effective properties of the medium inwhich the emitter material resides resulting in any or all of thefollowing: a decreased rate of emission, a modification of emissionline-shape, a change in emission intensity with angle, a change in thestability of the emitter material, a change in the efficiency of theOLED, and reduced efficiency roll-off of the OLED device. Placement ofthe enhancement layer on the cathode side, anode side, or on both sidesresults in OLED devices which take advantage of any of theabove-mentioned effects. In addition to the specific functional layersmentioned herein and illustrated in the various OLED examples shown inthe figures, the OLEDs according to the present disclosure may includeany of the other functional layers often found in OLEDs.

The enhancement layer can be comprised of plasmonic materials, opticallyactive metamaterials, or hyperbolic metamaterials. As used herein, aplasmonic material is a material in which the real part of thedielectric constant crosses zero in the visible or ultraviolet region ofthe electromagnetic spectrum. In some embodiments, the plasmonicmaterial includes at least one metal. In such embodiments the metal mayinclude at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg,Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials,and stacks of these materials. In general, a metamaterial is a mediumcomposed of different materials where the medium as a whole actsdifferently than the sum of its material parts. In particular, we defineoptically active metamaterials as materials which have both negativepermittivity and negative permeability. Hyperbolic metamaterials, on theother hand, are anisotropic media in which the permittivity orpermeability are of different sign for different spatial directions.Optically active metamaterials and hyperbolic metamaterials are strictlydistinguished from many other photonic structures such as DistributedBragg Reflectors (“DBRs”) in that the medium should appear uniform inthe direction of propagation on the length scale of the wavelength oflight. Using terminology that one skilled in the art can understand: thedielectric constant of the metamaterials in the direction of propagationcan be described with the effective medium approximation. Plasmonicmaterials and metamaterials provide methods for controlling thepropagation of light that can enhance OLED performance in a number ofways.

In some embodiments, the enhancement layer is provided as a planarlayer. In other embodiments, the enhancement layer has wavelength-sizedfeatures that are arranged periodically, quasi-periodically, orrandomly, or sub-wavelength-sized features that are arrangedperiodically, quasi-periodically, or randomly. In some embodiments, thewavelength-sized features and the sub-wavelength-sized features havesharp edges.

In some embodiments, the outcoupling layer has wavelength-sized featuresthat are arranged periodically, quasi-periodically, or randomly, orsub-wavelength-sized features that are arranged periodically,quasi-periodically, or randomly. In some embodiments, the outcouplinglayer may be composed of a plurality of nanoparticles and in otherembodiments the outcoupling layer is composed of a plurality ofnanoparticles disposed over a material. In these embodiments theoutcoupling may be tunable by at least one of varying a size of theplurality of nanoparticles, varying a shape of the plurality ofnanoparticles, changing a material of the plurality of nanoparticles,adjusting a thickness of the material, changing the refractive index ofthe material or an additional layer disposed on the plurality ofnanoparticles, varying a thickness of the enhancement layer, and/orvarying the material of the enhancement layer. The plurality ofnanoparticles of the device may be formed from at least one of metal,dielectric material, semiconductor materials, an alloy of metal, amixture of dielectric materials, a stack or layering of one or morematerials, and/or a core of one type of material and that is coated witha shell of a different type of material. In some embodiments, theoutcoupling layer is composed of at least metal nanoparticles whereinthe metal is selected from the group consisting of Ag, Al, Au, Ir, Pt,Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys ormixtures of these materials, and stacks of these materials. Theplurality of nanoparticles may have additional layer disposed over them.In some embodiments, the polarization of the emission can be tuned usingthe outcoupling layer. Varying the dimensionality and periodicity of theoutcoupling layer can select a type of polarization that ispreferentially outcoupled to air. In some embodiments the outcouplinglayer also acts as an electrode of the device.

In yet another aspect, the present disclosure also provides a consumerproduct comprising an organic light-emitting device (OLED) having ananode; a cathode; and an organic layer disposed between the anode andthe cathode, wherein the organic layer may comprise a compound asdisclosed in the above compounds section of the present disclosure.

In some embodiments, the consumer product comprises an OLED having ananode; a cathode; and an organic layer disposed between the anode andthe cathode, wherein the organic layer can comprise a compoundcomprising a ligand L_(A) of Formula I described herein.

In some embodiments, the consumer product can be one of a flat paneldisplay, a computer monitor, a medical monitor, a television, abillboard, a light for interior or exterior illumination and/orsignaling, a heads-up display, a fully or partially transparent display,a flexible display, a laser printer, a telephone, a cell phone, tablet,a phablet, a personal digital assistant (PDA), a wearable device, alaptop computer, a digital camera, a camcorder, a viewfinder, amicro-display that is less than 2 inches diagonal, a 3-D display, avirtual reality or augmented reality display, a vehicle, a video wallcomprising multiple displays tiled together, a theater or stadiumscreen, a light therapy device, and a sign.

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

Several OLED materials and configurations are described in U.S. Pat.Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated hereinby reference in their entirety.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated byreference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe present disclosure may be used in connection with a wide variety ofother structures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink-jet and organic vaporjet printing (OVJP). Other methods may also be used. The materials to bedeposited may be modified to make them compatible with a particulardeposition method. For example, substituents such as alkyl and arylgroups, branched or unbranched, and preferably containing at least 3carbons, may be used in small molecules to enhance their ability toundergo solution processing. Substituents having 20 carbons or more maybe used, and 3-20 carbons are a preferred range. Materials withasymmetric structures may have better solution processability than thosehaving symmetric structures, because asymmetric materials may have alower tendency to recrystallize. Dendrimer substituents may be used toenhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentdisclosure may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the presentdisclosure can be incorporated into a wide variety of electroniccomponent modules (or units) that can be incorporated into a variety ofelectronic products or intermediate components. Examples of suchelectronic products or intermediate components include display screens,lighting devices such as discrete light source devices or lightingpanels, etc. that can be utilized by the end-user product manufacturers.Such electronic component modules can optionally include the drivingelectronics and/or power source(s). Devices fabricated in accordancewith embodiments of the present disclosure can be incorporated into awide variety of consumer products that have one or more of theelectronic component modules (or units) incorporated therein. A consumerproduct comprising an OLED that includes the compound of the presentdisclosure in the organic layer in the OLED is disclosed. Such consumerproducts would include any kind of products that include one or morelight source(s) and/or one or more of some type of visual displays. Someexamples of such consumer products include flat panel displays, curveddisplays, computer monitors, medical monitors, televisions, billboards,lights for interior or exterior illumination and/or signaling, heads-updisplays, fully or partially transparent displays, flexible displays,rollable displays, foldable displays, stretchable displays, laserprinters, telephones, mobile phones, tablets, phablets, personal digitalassistants (PDAs), wearable devices, laptop computers, digital cameras,camcorders, viewfinders, micro-displays (displays that are less than 2inches diagonal), 3-D displays, virtual reality or augmented realitydisplays, vehicles, video walls comprising multiple displays tiledtogether, theater or stadium screen, a light therapy device, and a sign.Various control mechanisms may be used to control devices fabricated inaccordance with the present disclosure, including passive matrix andactive matrix. Many of the devices are intended for use in a temperaturerange comfortable to humans, such as 18 degrees C. to 30 degrees C., andmore preferably at room temperature (20-25° C.), but could be usedoutside this temperature range, for example, from −40 degree C. to +80°C.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

In some embodiments, the OLED has one or more characteristics selectedfrom the group consisting of being flexible, being rollable, beingfoldable, being stretchable, and being curved. In some embodiments, theOLED is transparent or semi-transparent. In some embodiments, the OLEDfurther comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising adelayed fluorescent emitter. In some embodiments, the OLED comprises aRGB pixel arrangement or white plus color filter pixel arrangement. Insome embodiments, the OLED is a mobile device, a hand held device, or awearable device. In some embodiments, the OLED is a display panel havingless than 10 inch diagonal or 50 square inch area. In some embodiments,the OLED is a display panel having at least 10 inch diagonal or 50square inch area. In some embodiments, the OLED is a lighting panel.

In some embodiments, the compound can be an emissive dopant. In someembodiments, the compound can produce emissions via phosphorescence,fluorescence, thermally activated delayed fluorescence, i.e., TADF (alsoreferred to as E-type delayed fluorescence; see, e.g., U.S. applicationSer. No. 15/700,352, which is hereby incorporated by reference in itsentirety), triplet-triplet annihilation, or combinations of theseprocesses. In some embodiments, the emissive dopant can be a racemicmixture, or can be enriched in one enantiomer. In some embodiments, thecompound can be homoleptic (each ligand is the same). In someembodiments, the compound can be heteroleptic (at least one ligand isdifferent from others). When there are more than one ligand coordinatedto a metal, the ligands can all be the same in some embodiments. In someother embodiments, at least one ligand is different from the otherligands. In some embodiments, every ligand can be different from eachother. This is also true in embodiments where a ligand being coordinatedto a metal can be linked with other ligands being coordinated to thatmetal to form a tridentate, tetradentate, pentadentate, or hexadentateligands. Thus, where the coordinating ligands are being linked together,all of the ligands can be the same in some embodiments, and at least oneof the ligands being linked can be different from the other ligand(s) insome other embodiments.

In some embodiments, the compound can be used as a phosphorescentsensitizer in an OLED where one or multiple layers in the OLED containsan acceptor in the form of one or more fluorescent and/or delayedfluorescence emitters. In some embodiments, the compound can be used asone component of an exciplex to be used as a sensitizer. As aphosphorescent sensitizer, the compound must be capable of energytransfer to the acceptor and the acceptor will emit the energy orfurther transfer energy to a final emitter. The acceptor concentrationscan range from 0.001% to 100%. The acceptor could be in either the samelayer as the phosphorescent sensitizer or in one or more differentlayers. In some embodiments, the acceptor is a TADF emitter. In someembodiments, the acceptor is a fluorescent emitter. In some embodiments,the emission can arise from any or all of the sensitizer, acceptor, andfinal emitter.

According to another aspect, a formulation comprising the compounddescribed herein is also disclosed.

The OLED disclosed herein can be incorporated into one or more of aconsumer product, an electronic component module, and a lighting panel.The organic layer can be an emissive layer and the compound can be anemissive dopant in some embodiments, while the compound can be anon-emissive dopant in other embodiments.

In yet another aspect of the present disclosure, a formulation thatcomprises the novel compound disclosed herein is described. Theformulation can include one or more components selected from the groupconsisting of a solvent, a host, a hole injection material, holetransport material, electron blocking material, hole blocking material,and an electron transport material, disclosed herein.

The present disclosure encompasses any chemical structure comprising thenovel compound of the present disclosure, or a monovalent or polyvalentvariant thereof. In other words, the inventive compound, or a monovalentor polyvalent variant thereof, can be a part of a larger chemicalstructure. Such chemical structure can be selected from the groupconsisting of a monomer, a polymer, a macromolecule, and a supramolecule(also known as supermolecule). As used herein, a “monovalent variant ofa compound” refers to a moiety that is identical to the compound exceptthat one hydrogen has been removed and replaced with a bond to the restof the chemical structure. As used herein, a “polyvalent variant of acompound” refers to a moiety that is identical to the compound exceptthat more than one hydrogen has been removed and replaced with a bond orbonds to the rest of the chemical structure. In the instance of asupramolecule, the inventive compound can also be incorporated into thesupramolecule complex without covalent bonds.

D. Combination of the Compounds of the Present Disclosure with OtherMaterials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

a) Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants tosubstantially alter its density of charge carriers, which will in turnalter its conductivity. The conductivity is increased by generatingcharge carriers in the matrix material, and depending on the type ofdopant, a change in the Fermi level of the semiconductor may also beachieved. Hole-transporting layer can be doped by p-type conductivitydopants and n-type conductivity dopants are used in theelectron-transporting layer.

Non-limiting examples of the conductivity dopants that may be used in anOLED in combination with materials disclosed herein are exemplifiedbelow together with references that disclose those materials:EP01617493, EP01968131, EP2020694, EP2684932, US20050139810,US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455,WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804,US20150123047, and US2012146012.

b) HIL/HTL:

A hole injecting/transporting material to be used in the presentdisclosure is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but are not limited to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, butnot limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, and azulene; the group consistingof aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and the group consisting of 2 to 10 cyclic structural units which aregroups of the same type or different types selected from the aromatichydrocarbon cyclic group and the aromatic heterocyclic group and arebonded to each other directly or via at least one of oxygen atom,nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom,chain structural unit and the aliphatic cyclic group. Each Ar may beunsubstituted or may be substituted by a substituent selected from thegroup consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylicacids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are notlimited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Non-limiting examples of the HIL and HTL materials that may be used inan OLED in combination with materials disclosed herein are exemplifiedbelow together with references that disclose those materials:CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334,EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701,EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765,JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473,TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053,US20050123751, US20060182993, US20060240279, US20070145888,US20070181874, US20070278938, US20080014464, US20080091025,US20080106190, US20080124572, US20080145707, US20080220265,US20080233434, US20080303417, US2008107919, US20090115320,US20090167161, US2009066235, US2011007385, US20110163302, US2011240968,US2011278551, US2012205642, US2013241401, US20140117329, US2014183517,U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550,WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006,WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577,WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937,WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.

c) EBL:

An electron blocking layer (EBL) may be used to reduce the number ofelectrons and/or excitons that leave the emissive layer. The presence ofsuch a blocking layer in a device may result in substantially higherefficiencies, and/or longer lifetime, as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the EBLmaterial has a higher LUMO (closer to the vacuum level) and/or highertriplet energy than the emitter closest to the EBL interface. In someembodiments, the EBL material has a higher LUMO (closer to the vacuumlevel) and/or higher triplet energy than one or more of the hostsclosest to the EBL interface. In one aspect, the compound used in EBLcontains the same molecule or the same functional groups used as one ofthe hosts described below.

d) Hosts:

The light emitting layer of the organic EL device of the presentdisclosure preferably contains at least a metal complex as lightemitting material, and may contain a host material using the metalcomplex as a dopant material. Examples of the host material are notparticularly limited, and any metal complexes or organic compounds maybe used as long as the triplet energy of the host is larger than that ofthe dopant. Any host material may be used with any dopant so long as thetriplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

In one aspect, the host compound contains at least one of the followinggroups selected from the group consisting of aromatic hydrocarbon cycliccompounds such as benzene, biphenyl, triphenyl, triphenylene,tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, and azulene; the group consistingof aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and the group consisting of 2 to 10 cyclic structural units which aregroups of the same type or different types selected from the aromatichydrocarbon cyclic group and the aromatic heterocyclic group and arebonded to each other directly or via at least one of oxygen atom,nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom,chain structural unit and the aliphatic cyclic group. Each option withineach group may be unsubstituted or may be substituted by a substituentselected from the group consisting of deuterium, halogen, alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains at least one of the followinggroups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof, and when it is aryl or heteroaryl, it has thesimilar definition as Ar's mentioned above. k is an integer from 0 to 20or 1 to 20. X¹⁰¹ to X¹⁰⁸ are independently selected from C (includingCH) or N. Z¹⁰¹ and Z¹⁰² are independently selected from NR¹⁰¹, O, or S.

Non-limiting examples of the host materials that may be used in an OLEDin combination with materials disclosed herein are exemplified belowtogether with references that disclose those materials: EP2034538,EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644,KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919,US20060280965, US20090017330, US20090030202, US20090167162,US20090302743, US20090309488, US20100012931, US20100084966,US20100187984, US2010187984, US2012075273, US2012126221, US2013009543,US2013105787, US2013175519, US2014001446, US20140183503, US20140225088,US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207,WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754,WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778,WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423,WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649,WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,US20170263869, US20160163995, U.S. Pat. No. 9,466,803,

e) Additional Emitters:

One or more additional emitter dopants may be used in conjunction withthe compound of the present disclosure. Examples of the additionalemitter dopants are not particularly limited, and any compounds may beused as long as the compounds are typically used as emitter materials.Examples of suitable emitter materials include, but are not limited to,compounds which can produce emissions via phosphorescence, fluorescence,thermally activated delayed fluorescence, i.e., TADF (also referred toas E-type delayed fluorescence), triplet-triplet annihilation, orcombinations of these processes.

Non-limiting examples of the emitter materials that may be used in anOLED in combination with materials disclosed herein are exemplifiedbelow together with references that disclose those materials:CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526,EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907,EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652,KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599,U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526,US20030072964, US20030138657, US20050123788, US20050244673,US2005123791, US2005260449, US20060008670, US20060065890, US20060127696,US20060134459, US20060134462, US20060202194, US20060251923,US20070034863, US20070087321, US20070103060, US20070111026,US20070190359, US20070231600, US2007034863, US2007104979, US2007104980,US2007138437, US2007224450, US2007278936, US20080020237, US20080233410,US20080261076, US20080297033, US200805851, US2008161567, US2008210930,US20090039776, US20090108737, US20090115322, US20090179555,US2009085476, US2009104472, US20100090591, US20100148663, US20100244004,US20100295032, US2010102716, US2010105902, US2010244004, US2010270916,US20110057559, US20110108822, US20110204333, US2011215710, US2011227049,US2011285275, US2012292601, US20130146848, US2013033172, US2013165653,US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos.6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469,6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228,7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586,8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970,WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373,WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842,WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731,WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491,WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471,WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977,WO2014038456, WO2014112450.

f) HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies and/or longer lifetime as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the HBLmaterial has a lower HOMO (further from the vacuum level) and/or highertriplet energy than the emitter closest to the HBL interface. In someembodiments, the HBL material has a lower HOMO (further from the vacuumlevel) and/or higher triplet energy than one or more of the hostsclosest to the HBL interface.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is another ligand, k′ is aninteger from 1 to 3.

g) ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof, when it is aryl or heteroaryl, it has the similardefinition as Ar's mentioned above. Ar¹ to Ar³ has the similardefinition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹to X¹⁰⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but notlimit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

Non-limiting examples of the ETL materials that may be used in an OLEDin combination with materials disclosed herein are exemplified belowtogether with references that disclose those materials: CN103508940,EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918,JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977,US2007018155, US20090101870, US20090115316, US20090140637,US20090179554, US2009218940, US2010108990, US2011156017, US2011210320,US2012193612, US2012214993, US2014014925, US2014014927, US20140284580,U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263,WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373,WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in theperformance, which is composed of an n-doped layer and a p-doped layerfor injection of electrons and holes, respectively. Electrons and holesare supplied from the CGL and electrodes. The consumed electrons andholes in the CGL are refilled by the electrons and holes injected fromthe cathode and anode, respectively; then, the bipolar currents reach asteady state gradually. Typical CGL materials include n and pconductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. may be undeuterated, partially deuterated, andfully deuterated versions thereof. Similarly, classes of substituentssuch as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.also may be undeuterated, partially deuterated, and fully deuteratedversions thereof.

It is understood that the various embodiments described herein are byway of example only and are not intended to limit the scope of theinvention. For example, many of the materials and structures describedherein may be substituted with other materials and structures withoutdeviating from the spirit of the invention. The present invention asclaimed may therefore include variations from the particular examplesand preferred embodiments described herein, as will be apparent to oneof skill in the art. It is understood that various theories as to whythe invention works are not intended to be limiting.

E. Experimental Data Synthesis of 2-(Benzyloxy)-6-fluorobenzaldehyde (1)

A mixture of 2-fluoro-6-hydroxybenzaldehyde (25.0 g, 178 mmol), K₂CO₃(74.0 g, 535 mmol) and benzyl bromide (32 mL, 270 mmol) in dry MeCN (500mL) under nitrogen was stirred for 18 hours at room temperature (RT).The mixture was filtered, rinsed through with EtOAc (2×150 mL) and thefiltrate was concentrated in vacuo. Purification by chromatography gave2-(benzyloxy)-6-fluorobenzaldehyde (1) (28.5 g, 123 mmol, 69%yield, >98% purity) as a colourless liquid, which crystallized onstanding.

Synthesis of 2-(2-(Benzyloxy)-6-fluorophenyl)-1H-imidazole (2)

Ammonia (28 wt % in H₂O) (100 mL, 1.29 mol) was added to a stirredmixture of glyoxal (40 wt % in H₂O) (75 mL, 0.65 mol) and2-(benzyloxy)-6-fluorobenzaldehyde (1) (28.5 g, 123 mmol) in EtOH (350mL). The reaction mixture was stirred at 50° C. for 19 hours. Furtherglyoxal (40 wt % in H₂O) (12.0 mL, 262 mmol) was added and the mixturewas stirred at 50° C. for 3 hours. The mixture was cooled to RT andconcentrated in vacuo. The residue was purified in three equal batchesby column chromatography to give a dark brown solid. This solid wastriturated with TBME (300 mL), filtered, rinsed with MTBE (2×100 mL) anddried in vacuo to give 2-(2-(benzyloxy)-6-fluorophenyl)-1H-imidazole (2)(16.5 g, 60.3 mmol, 49% yield, >98% purity) as a light brown powder.

Synthesis of 3-(Benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3)

A mixture of isopropylmagnesium chloride (2 M in THF, 150 mL, 300 mmol)in diglyme (300 mL) was cooled to 0° C. and methylamine (2 M in THF, 120mL, 240 mmol) was added over 5 min. The resulting mixture was stirred at0° C. for 1 hour, then a suspension of2-(2-(benzyloxy)-6-fluorophenyl)-1H-imidazole (2) (16.5 g, 60.3 mmol) indiglyme (300 mL) was added over 20 min. The resulting mixture was heatedto 110° C. and stirred for 22 hours. The mixture was poured into sat.NH₄Cl(aq) (600 mL), diluted with EtOAc (200 mL) and sonicated for 2 min.The layers were separated and the aqueous phase was extracted with EtOAc(3×300 mL). The combined organic extracts were washed with brine (400mL), dried over MgSO₄, filtered and concentrated in vacuo. Purificationby column chromatography gave3-(benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3) (11.4 g, 36.7mmol, 61% yield, 90% purity) as a pale yellow solid.

Synthesis of 2-(1H-Imidazol-2-yl)-3-(methylamino)phenol (4)

A mixture of 3-(benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3)(11.4 g, 36.7 mmol) and Pd (10% on C, wetted with 50% water, 1.9 g, 0.69mmol) in EtOH (150 mL) and THF (80 mL) was stirred in a steel bomb underhydrogen (2 bar) at RT for 2 hours. The mixture was filtered (GF/F glassmicrofibre pad) and concentrated in vacuo. Purification by columnchromatography gave 2-(1H-imidazol-2-yl)-3-(methylamino)phenol (4) (5.46g, 28.3 mmol, 77% yield, >98% purity) as a brown solid.

Synthesis of5-(2,6-Diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinin-10-ol(5)

TMSCl (4.30 mL, 33.6 mmol) was added to solution of potassium(2,6-diisopropylphenyl)trifluoroborate (9.00 g, 33.6 mmol) in dry THF(30 mL) under nitrogen. The resulting mixture was stirred at RT for 1hour [Solution A].

In a separate flask, n-BuLi (2.5 M in hexanes, 20 mL, 50 mmol) was addeda solution of 2-(1H-imidazol-2-yl)-3-(methylamino)phenol (4) (3.00 g,15.9 mmol) in dry THF (30 mL) under nitrogen at −78° C. The resultingmixture was stirred at −78° C. for 1 hour [Solution B].

Solution A was added to Solution B at −78° C. over 10 min. The mixturewas warmed to RT, then stirred at 60° C. for 1 hour. The mixture wascooled to RT, quenched with sat. NH₄Cl(aq) (60 mL) and diluted withwater(60 mL). The aqueous layer was extracted with EtOAc (120 mL, 3×60mL) and the combined organic extracts were washed with brine (120 mL),dried over MgSO₄, filtered and concentrated in vacuo. Purification bycolumn chromatography gave the product as a white powder (4.6 g, <98%purity). This material was triturated with TBME (20 mL) and the solidwas collected by filtration, rinsed with TBME (2×5 mL) and dried invacuo to give5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinin-10-ol (5) (2.63 g, 7.31 mmol, 46% yield, 99.6% HPLC) as awhite powder.

Synthesis of Phosphorescent Complexes

A heterogeneous mixture of [IrL₂Cl]₂ (1 equiv., 0.02 M), (5) (2.2equiv.), and K₂C₃ (10 equiv.) in THF was stirred at 60° C. undernitrogen for two days. Solvent was removed in vacuo and the cruderesidue was purified by column chromatography, yielding the products in35-65% yields.

TABLE 1 Photophysical Properties of Inventive Compounds: λ_(max) λ_(max)λmax PLQY Compound Structure (77K) (RT) (PMMA) (PMMA) Ir[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂

467 478 477  85% Ir[L_(A)1- (33)(2)(1)(1)][L_(B28)]₂

499 516 510 100% Ir[L_(A)1- (33)(2)(1)(1)][L_(B540)]₂

602 630 624  80%

Photolumnescent spectra of inventive complexesIr[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂, Ir[L_(A)1-(33)(2)(1)(1)][L_(B28)]₂and Ir[L_(A)1-(33)(2)(1)(1)][L_(B540)]₂ are showing in FIGS. 3-5. As thespectra of complexes Ir[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂,Ir[L_(A)1-(33)(2)(1)(1)][L_(B28)]₂, andIr[L_(A)1-(33)(2)(1)(1)][L_(B540)]₂ show, the inventive compounds pairfavorably with multiple emissive ligand classes in phosphorescentcomplexes. The inventive compounds support high-efficiency emissionacross the visible spectrum, and their ease of metalation makes themattractive ligands by which photophysical, electroluminescent, andphysical properties can be tuned to best suit their intendedapplication.

Device Experimental

Device 1:

OLEDs were grown on a glass substrate pre-coated with anindium-tin-oxide (ITO) layer having a sheet resistance of 15-Ω/sq. Priorto any organic layer deposition or coating, the substrate was degreasedwith solvents and then treated with an oxygen plasma for 1.5 minuteswith 50W at 100 mTorr and with UV ozone for 5 minutes.

The devices in Tables 1 were fabricated in high vacuum (<10-6 Torr) bythermal evaporation. The anode electrode was 750 Å of indium tin oxide(ITO). The device example had organic layers consisting of,sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 250 Å ofCompound 2 (HTL), 50 Å of Compound 3 (EBL), 300 Å of Compound 4 dopedwith a percentage of Emitter (EML), 50 Å of Compound 5 (BL), 300 Å ofCompound 6 (ETL), 10 Å of Compound 7 (EIL) followed by 1,000 Å of A1(Cathode). All devices were encapsulated with a glass lid sealed with anepoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediatelyafter fabrication with a moisture getter incorporated inside thepackage. Doping percentages are in volume percent.

TABLE 2 at 10 mA/cm² LT₉₀ λ 20 Emitter 1931 CIE max FWHM Voltage EQEmA/cm² Device Emitter [%] x y [nm] [nm] [norm] [norm] [norm] 1Ir[L_(A)1- 20 0.194 0.463 481 58 0.85 1.32 2.7 (33)(2)(1)(1)][L_(B148)]₂Comparative 1 20 0.193 0.444 479 57 1.00 1.00 1.0

Device 2:

OLEDs were grown on a glass substrate pre-coated with anindium-tin-oxide (ITO) layer having a sheet resistance of 15-Ω/sq. Priorto any organic layer deposition or coating, the substrate was degreasedwith solvents and then treated with an oxygen plasma for 1.5 minuteswith 50W at 100 mTorr and with UV ozone for 5 minutes.

The devices in Tables 2 were fabricated in high vacuum (<10-6 Torr) bythermal evaporation. The anode electrode was 750 Å of indium tin oxide(ITO). The device example had organic layers consisting of,sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 400 Å ofCompound 2 (HTL), 50 Å of Compound 3 (EBL), 400 Å of Compound 8 dopedwith Compound 9 (35%) and a percentage of Emitter (EML), 350 Å ofCompound 7 doped with Compound 10 (35%) (ETL), 10 Å of Compound 7 (EIL)followed by 1,000 Å of A1 (Cathode). All devices were encapsulated witha glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppmof H₂O and O₂) immediately after fabrication with a moisture getterincorporated inside the package. Doping percentages are in volumepercent.

TABLE 3 at 10 mA/cm² LT₉₀ λ 80 Emitter 1931 CIE max FWHM Voltage EQEmA/cm² Device Emitter [%] x y [nm] [nm] [norm] [norm] [norm] 2Ir[L_(A)1- 12 0.333 0.625 524 69 0.93 0.92 1.05 (33)(2)(1)(1)][L_(B28)]₂Comparative 2 12 0.316 0.636 520 64 1.00 1.00 1.00

The electroluminescent device data for bothIr[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂ andIr[L_(A)1-(33)(2)(1)(1)][L_(B28)]₂ also support the benefit of employingthe inventive compounds in phosphorescent materials. Not only are theelectroluminescent lifetimes maintained when normalized againstinventive compounds, but in the case ofIr[L_(A)1-(33)(2)(1)(1)][L_(B148)]₂ are improved 2.7-fold. And while thespectral behavior between the inventive and comparative compounds arecomparable, there is a reduction in operating voltage as high as 15%,making the inventive ligands effective tools in the design andmanufacture of high-efficiency, long-lifetime OLED devices.

1.-72. (canceled)
 73. A compound comprising a ligand L_(A) of Formula I:

wherein: each of Z¹, Z², Z³, Z⁴, Z⁵, and Z⁶ each independently C or N; Kis selected from the group consisting of a direct bond, O, and S; when Kis O or S, then Z⁶ is C; each of ring A1 and ring A2 is independently a5-membered or 6-membered carbocyclic or heterocyclic rings or amulticyclic fused-ring system comprising more than one 5-membered or6-membered carbocyclic or heterocyclic ring; each of R^(A) and R^(B) isindependently mono, up to a maximum allowed substitutions, or nosubstitution; the ligand L_(A) is coordinated to a metal M by the twoindicated dash lines; M is selected from the group consisting of Ru, Os,Ir, Pd, Pt, Cu, Ag, and Au; M is coordinated to at least one otherligand; L_(A) can be joined with other ligands to form a tridentate,tetradentate, pentadentate, or hexadentate ligand; L¹ is an organiclinker, when M is selected from the group consisting of Ru, Os, and Ir,then K is O or S; when M is selected from the group consisting of Pt,Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least onebond to oxygen or sulfur; and when M is selected from the groupconsisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then LI isselected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—,—CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR₂—,—C(═N—)—, and —C(═CR—)—; each R^(A), R^(B), R, R′, R″ is independently ahydrogen or a substituent selected from the group consisting ofdeuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and any two adjacent R^(A), R^(B), R, R′ and R″can be joined or fused together to form a ring.
 74. The compound ofclaim 73, wherein each R^(A), R^(B), R, R′, R″ is independently ahydrogen or a substituent selected from the group consisting ofdeuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy,amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl,heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof. 75.The compound of claim 73, wherein Z³ is selected from the groupconsisting of N and carbene carbon; and either Z⁶ is C and K is O or S;or Z⁶ is N and K is a direct bond.
 76. The compound of claim 73, whereinring A1 is selected from the group consisting of imidazole,benzimidazole, imidazole-based carbene, benzimidazole-based carbene,pyrimidine, pyrazole, and pyridine; and ring A2 is selected from thegroup consisting of benzene, pyridine, carbazole, benzimidazole,benzothiophene, dibenzothiophene, benzofuran, dibenzofuran,dibenzofluorene, naphthalene, tetrahydronaphthalene, phenoxazine,9,10-dihydroacridine, anthracene, and phenanthrene.
 77. The compound ofclaim 73, wherein M is selected from the group consisting of Ru, Os, andIr, and K is O or S.
 78. The compound of claim 73, wherein the organiclinker L¹ is selected from the group consisting of —X—, —X—X′—,—X^(L)═X^(L′)—, and —X^(L)═X^(L′)—X—; wherein X and X′ are eachindependently selected from the group consisting of BR′, NR′, PR′, O, S,Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; and X^(L) and X^(L′) areeach independently selected from the group consisting of N and CR′. 79.The compound of claim 73, wherein M is selected from the groupconsisting of Pt, Pd, Cu, Ag, or Au, and K is a direct bond; and whereinthe organic linker L¹ is selected from the group consisting of —X—,—X—X′—, —X^(L)═X^(L′), and —X^(L)═X^(L′)—X—, wherein X and X′ are eachindependently selected from the group consisting of BR′, NR′, PR′, O, S,Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; and X^(L) and X^(L′) areeach independently selected from the group consisting of N and CR′. 80.The compound of claim 73, wherein M is selected from the groupconsisting of Pt, Pd, Cu, Ag, or Au, and K is S or O; wherein L¹ isselected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—,—CR′R″O—, and —CR′R″S—.
 81. The compound of claim 73, wherein the ligandL_(A) is selected from the group consisting of:

and wherein each R^(A), R^(B), R^(C), R¹, R², R³, and R⁴ isindependently a hydrogen or a substituent selected from the groupconsisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl,heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylicacid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, boryl, and combinations thereof.
 82. The compound of claim73, wherein the compound has a formula ofM(L_(A))_(p)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each abidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0,1, or 2; and p+q+r is the oxidation state of the metal M.
 83. Thecompound of claim 82, wherein L_(B) and L_(C) are each independentlyselected from the group consisting of:

wherein: T is selected from the group consisting of B, Al, Ga, and In;each of Y¹ to Y¹³ is independently selected from the group consisting ofcarbon and nitrogen; Y′ is selected from the group consisting of BR_(e),NR_(e), PR_(e), O, S, Se, C═O, S═O, SO₂, CR_(e)R_(f), SiR_(e)R_(f), andGeR_(e)R_(f); R_(e) and R_(f) can be fused or joined to form a ring;each R_(a), R_(b), R_(c) and R_(d) independently represents zero, mono,or up to a maximum allowed number of substitutions to its associatedring; each of R_(a1), R_(b1), R_(c1), R_(d1), R_(a), R_(b), R_(c),R_(d), R_(e) and R_(f) is independently a hydrogen or a substituentselected from the group consisting of deuterium, halide, alkyl,cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl,boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl,acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl,sulfinyl, sulfonyl, phosphino, and combinations thereof; the generalsubstituents defined herein; and any two adjacent R_(a), R_(b), R_(c),R_(d), R_(e) and R_(f) can be fused or joined to form a ring or form amultidentate ligand.
 84. The compound of claim 82, wherein when thecompound has formula Ir(L_(A))₃, L_(A) is selected from the groupconsisting of the structures in the following group referred to asL_(A,spec), wherein each of i, j, k, and l is independently an integerfrom 1 to 86: L_(A) Structure of L_(A) DefinitionsL_(A)1-(Ri)(Rj)(Rk)(Rl), where L_(A)1- (R1)(R1)(R1)(R1) to L_(A)1-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)2-(Ri)(Rj)(Rk)(Rl), where L_(A)2- (R1)(R1)(R1)(R1) to L_(A)2-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)3-(Ri)(Rj)(Rk)(Rl), L_(A)3-(R1)(R1)(R1)(R1) toL_(A)3-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)4-(Ri)(Rj)(Rk)(Rl), L_(A)4-(R1)(R1)(R1)(R1) toL_(A)4-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)5-(Ri)(Rj)(Rk)(Rl), L_(A)5-(R1)(R1)(R1)(R1) toL_(A)5-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)6-(Ri)(Rj)(Rk)(Rl), L_(A)6-(R1)(R1)(R1)(R1) toL_(A)6-(R86)(R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, R^(A3) is Rk, R^(A4) is Rl,L_(A)7-(Ri)(Rj), L_(A)7-(R1)(R1) to L_(A)7-(R86)(R86) have thestructure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)8-(Ri)(Rj), L_(A)8-(R1)(R1)to L_(A)8-(R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)9-(Ri)(Rj), L_(A)9-(R1)(R1)to L_(A)9-(R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)10-(Ri)(Rj),L_(A)10-(R1)(R1) to L_(A)10- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)11-(Ri)(Rj),L_(A)11-(R1)(R1) to L_(A)11- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)12-(Ri)(Rj),L_(A)12-(R1)(R1) to L_(A)12- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)13-(Ri)(Rj),L_(A)13-(R1)(R1) to L_(A)13- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)14-(Ri)(Rj),L_(A)14-(R1)(R1) to L_(A)14- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)15-(Ri)(Rj),L_(A)15-(R1)(R1) to L_(A)15- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)16-(Ri)(Rj),L_(A)16-(R1)(R1) to L_(A)16- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)17-(Ri)(Rj),L_(A)17-(R1)(R1) to L_(A)17- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)18-(Ri)(Rj),L_(A)18-(R1)(R1) to L_(A)18- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)19-(Ri)(Rj),L_(A)19-(R1)(R1) to L_(A)19- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)20-(Ri)(Rj),L_(A)20-(R1)(R1) to L_(A)20- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)21-(Ri)(Rj),L_(A)21-(R1)(R1) to L_(A)21- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)22-(Ri)(Rj),L_(A)22-(R1)(R1) to L_(A)22- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)23-(Ri)(Rj),L_(A)23-(R1)(R1) to L_(A)23- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)24-(Ri)(Rj),L_(A)24-(R1)(R1) to L_(A)24- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)25-(Ri)(Rj),L_(A)25-(R1)(R1) to L_(A)25- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)26-(Ri)(Rj),L_(A)26-(R1)(R1) to L_(A)26- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)27-(Ri)(Rj),L_(A)27-(R1)(R1) to L_(A)27- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)28-(Ri)(Rj),L_(A)28-(R1)(R1) to L_(A)28- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)29-(Ri)(Rj),L_(A)29-(R1)(R1) to L_(A)29- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)30-(Ri)(Rj),L_(A)30-(R1)(R1) to L_(A)30- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)31-(Ri)(Rj),L_(A)31-(R1)(R1) to L_(A)31- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)32-(Ri)(Rj),L_(A)32-(R1)(R1) to L_(A)32- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)33-(Ri)(Rj),L_(A)33-(R1)(R1) to L_(A)33- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)34-(Ri)(Rj),L_(A)34-(R1)(R1) to L_(A)34- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)35-(Ri)(Rj),L_(A)35-(R1)(R1) to L_(A)35- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)36-(Ri)(Rj),L_(A)36-(R1)(R1) to L_(A)36- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)37-(Ri)(Rj),L_(A)37-(R1)(R1) to L_(A)37- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)38-(Ri)(Rj),L_(A)38-(R1)(R1) to L_(A)38- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)39-(Ri)(Rj),L_(A)39-(R1)(R1) to L_(A)39- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)40-(Ri)(Rj),L_(A)40-(R1)(R1) to L_(A)40- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)41-(Ri)(Rj)(Rk),L_(A)41-(R1)(R1)(R1) to L_(A)41- (R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)42-(Ri)(Rj)(Rk), L_(A)42-(R1)(R1)(R1) to L_(A)42- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk, L_(A)43-(Ri)(Rj),L_(A)43-(R1)(R1) to L_(A)43- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)44-(Ri)(Rj),L_(A)44-(R1)(R1) to L_(A)44- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)45-(Ri)(Rj),L_(A)45-(R1)(R1) to L_(A)45- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)46-(Ri)(Rj),L_(A)46-(R1)(R1) to L_(A)46- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)47-(Ri)(Rj),L_(A)47-(R1)(R1) to L_(A)47- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)48-(Ri)(Rj),L_(A)48-(R1)(R1) to L_(A)48- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)49-(Ri)(Rj),L_(A)49-(R1)(R1) to L_(A)49- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)50-(Ri)(Rj),L_(A)50-(R1)(R1) to L_(A)50- (R86)(R86) have the structure,

wherein R^(A1) is Ri and R^(A2) is Rj, L_(A)51-(Ri)(Rj)(Rk),L_(A)51-(R1)(R1)(R1) to L_(A)51- (R86)(R86)(R86) have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)52-(Ri)(Rj)(Rk), L_(A)52-(R1)(R1)(R1) to L_(A)52- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)53-(Ri)(Rj)(Rk), L_(A)53-(R1)(R1)(R1) to L_(A)53- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)54-(Ri)(Rj)(Rk), L_(A)54-(R1)(R1)(R1) to L_(A)54- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)55-(Ri)(Rj)(Rk), L_(A)55-(R1)(R1)(R1) to L_(A)55- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)56-(Ri)(Rj)(Rk), L_(A)56-(R1)(R1)(R1) to L_(A)56- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)57-(Ri)(Rj)(Rk), L_(A)57-(R1)(R1)(R1) to L_(A)57- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)58-(Ri)(Rj)(Rk), L_(A)58-(R1)(R1)(R1) to L_(A)58- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)59-(Ri)(Rj)(Rk), L_(A)59-(R1)(R1)(R1) to L_(A)59- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)60-(Ri)(Rj)(Rk), L_(A)60-(R1)(R1)(R1) to L_(A)60- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)61-(Ri)(Rj)(Rk), L_(A)61-(R1)(R1)(R1) to L_(A)61- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)62-(Ri)(Rj)(Rk), L_(A)62-(R1)(R1)(R1) to L_(A)62- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)63-(Ri)(Rj)(Rk), L_(A)63-(R1)(R1)(R1) to L_(A)63- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk,L_(A)64-(Ri)(Rj)(Rk), L_(A)64-(R1)(R1)(R1) to L_(A)64- (R86)(R86)(R86)have the structure,

wherein R^(A1) is Ri, R^(A2) is Rj, and R^(A3) is Rk, L_(A)65-(Ri),L_(A)65-(R1) to L_(A)65-(R86) have the structure,

wherein R^(A1) is Ri, L_(A)66-(Ri), L_(A)66-(R1) to L_(A)66-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)67-(Ri), L_(A)67-(R1) to L_(A)67-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)68-(Ri), L_(A)68-(R1) to L_(A)68-(R86) havethe structure,

wherein R^(A1) is Ri, L_(A)69-(Ri), where L_(A)69-(R1) to L_(A)69-(R86)have the structure,

wherein R^(A1) is Ri, L_(A)70-(Ri), where L_(A)70-(R1) to L_(A)70-(R86)have the structure,

wherein R^(A1) is Ri, L_(A)71-(Ri), where L_(A)71-(R1) to L_(A)71-(R86)have the structure,

wherein R^(A1) is Ri,

wherein Ph represents phenyl; and wherein R1 to R86 have the followingstructures:

and the compound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₃ to Ir(L_(A)71-(R86))₃; when the compoundhas formula Ir(L_(A))(L_(Bk))₂, L_(A) is selected from the groupconsisting of the structures of L_(A,spec); k is an integer from 1 to540; and the compound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))(L_(B1))₂ to Ir(L_(A)71-(R86))(L_(B540))₂;when the compound has formula Ir(L_(Ai-m))₂(L_(Bk)), L_(A) is selectedfrom the group consisting of the structures of L_(A,spec); k is aninteger from 1 to 540; and the compound is selected from the groupconsisting of Ir(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(B1)) toIr(L_(A)71-(R86))₂(L_(B540)); when the compound has formulaIr(L_(Ai-m))₂(L_(Cj-I)), L_(A) is selected from the group consisting ofthe structures of L_(A,spec); j is an integer from 1 to 1416; and thecompound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(Cj-I)) toIr(L_(A)71-(R86))(L_(C1416-I)); and when the compound has formulaIr(L_(Ai-m))₂(L_(Cj-II)), L_(A) is selected from the group consisting ofthe structures of L_(A,spec); j is an integer from 1 to 1416; and thecompound is selected from the group consisting ofIr(L_(A)1-(R1)(R1)(R1)(R1))₂(L_(C1-II)) toIr(L_(A)71-(R86))(L_(C1416-II)); wherein L_(B1) to L_(B540) have thefollowing structures:

wherein each L_(Cj-I) has a structure based on formula

and each L_(Cj-II) has a structure based on formula

wherein for each L_(Cj) in L_(Cj-I) and L_(Cj-II), R²⁰¹ and R²⁰² areeach independently defined as follows: L_(Cj) R²⁰¹ R²⁰² L_(C1) R^(D1)R^(D1) L_(C2) R^(D2) R^(D2) L_(C3) R^(D3) R^(D3) L_(C4) R^(D4) R^(D4)L_(C5) R^(D5) R^(D5) L_(C6) R^(D6) R^(D6) L_(C7) R^(D7) R^(D7) L_(C8)R^(D8) R^(D8) L_(C9) R^(D9) R^(D9) L_(C10) R^(D10) R^(D10) L_(C11)R^(D11) R^(D11) L_(C12) R^(D12) R^(D12) L_(C13) R^(D13) R^(D13) L_(C14)R^(D14) R^(D14) L_(C15) R^(D15) R^(D15) L_(C16) R^(D16) R^(D16) L_(C17)R^(D17) R^(D17) L_(C18) R^(D18) R^(D18) L_(C19) R^(D19) R^(D19) L_(C20)R^(D20) R^(D20) L_(C21) R^(D21) R^(D21) L_(C22) R^(D22) R^(D22) L_(C23)R^(D23) R^(D23) L_(C24) R^(D24) R^(D24) L_(C25) R^(D25) R^(D25) L_(C26)R^(D26) R^(D26) L_(C27) R^(D27) R^(D27) L_(C28) R^(D28) R^(D28) L_(C29)R^(D29) R^(D29) L_(C30) R^(D30) R^(D30) L_(C31) R^(D31) R^(D31) L_(C32)R^(D32) R^(D32) L_(C33) R^(D33) R^(D33) L_(C34) R^(D34) R^(D34) L_(C35)R^(D35) R^(D35) L_(C36) R^(D36) R^(D36) L_(C37) R^(D37) R^(D37) L_(C38)R^(D38) R^(D38) L_(C39) R^(D39) R^(D39) L_(C40) R^(D40) R^(D40) L_(C41)R^(D41) R^(D41) L_(C42) R^(D42) R^(D42) L_(C43) R^(D43) R^(D43) L_(C44)R^(D44) R^(D44) L_(C45) R^(D45) R^(D45) L_(C46) R^(D46) R^(D46) L_(C47)R^(D47) R^(D47) L_(C48) R^(D48) R^(D48) L_(C49) R^(D49) R^(D49) L_(C50)R^(D50) R^(D50) L_(C51) R^(D51) R^(D51) L_(C52) R^(D52) R^(D52) L_(C53)R^(D53) R^(D53) L_(C54) R^(D54) R^(D54) L_(C55) R^(D55) R^(D55) L_(C56)R^(D56) R^(D56) L_(C57) R^(D57) R^(D57) L_(C58) R^(D58) R^(D58) L_(C59)R^(D59) R^(D59) L_(C60) R^(D60) R^(D60) L_(C61) R^(D61) R^(D61) L_(C62)R^(D62) R^(D62) L_(C63) R^(D63) R^(D63) L_(C64) R^(D64) R^(D64) L_(C65)R^(D65) R^(D65) L_(C66) R^(D66) R^(D66) L_(C67) R^(D67) R^(D67) L_(C68)R^(D68) R^(D68) L_(C69) R^(D69) R^(D69) L_(C70) R^(D70) R^(D70) L_(C71)R^(D71) R^(D71) L_(C72) R^(D72) R^(D72) L_(C73) R^(D73) R^(D73) L_(C74)R^(D74) R^(D74) L_(C75) R^(D75) R^(D75) L_(C76) R^(D76) R^(D76) L_(C77)R^(D77) R^(D77) L_(C78) R^(D78) R^(D78) L_(C79) R^(D79) R^(D79) L_(C80)R^(D80) R^(D80) L_(C81) R^(D81) R^(D81) L_(C82) R^(D82) R^(D82) L_(C83)R^(D83) R^(D83) L_(C84) R^(D84) R^(D84) L_(C85) R^(D85) R^(D85) L_(C86)R^(D86) R^(D86) L_(C87) R^(D87) R^(D87) L_(C88) R^(D88) R^(D88) L_(C89)R^(D89) R^(D89) L_(C90) R^(D90) R^(D90) L_(C91) R^(D91) R^(D91) L_(C92)R^(D92) R^(D92) L_(C93) R^(D93) R^(D93) L_(C94) R^(D94) R^(D94) L_(C95)R^(D95) R^(D95) L_(C96) R^(D96) R^(D96) L_(C97) R^(D97) R^(D97) L_(C98)R^(D98) R^(D98) L_(C99) R^(D99) R^(D99) L_(C100) R^(D100) R^(D100)L_(C101) R^(D101) R^(D101) L_(C102) R^(D102) R^(D102) L_(C103) R^(D103)R^(D103) L_(C104) R^(D104) R^(D104) L_(C105) R^(D105) R^(D105) L_(C106)R^(D106) R^(D106) L_(C107) R^(D107) R^(D107) L_(C108) R^(D108) R^(D108)L_(C109) R^(D109) R^(D109) L_(C110) R^(D110) R^(D110) L_(C111) R^(D111)R^(D111) L_(C112) R^(D112) R^(D112) L_(C113) R^(D113) R^(D113) L_(C114)R^(D114) R^(D114) L_(C115) R^(D115) R^(D115) L_(C116) R^(D116) R^(D116)L_(C117) R^(D117) R^(D117) L_(C118) R^(D118) R^(D118) L_(C119) R^(D119)R^(D119) L_(C120) R^(D120) R^(D120) L_(C121) R^(D121) R^(D121) L_(C122)R^(D122) R^(D122) L_(C123) R^(D123) R^(D123) L_(C124) R^(D124) R^(D124)L_(C125) R^(D125) R^(D125) L_(C126) R^(D126) R^(D126) L_(C127) R^(D127)R^(D127) L_(C128) R^(D128) R^(D128) L_(C129) R^(D129) R^(D129) L_(C130)R^(D130) R^(D130) L_(C131) R^(D131) R^(D131) L_(C132) R^(D132) R^(D132)L_(C133) R^(D133) R^(D133) L_(C134) R^(D134) R^(D134) L_(C135) R^(D135)R^(D135) L_(C136) R^(D136) R^(D136) L_(C137) R^(D137) R^(D137) L_(C138)R^(D138) R^(D138) L_(C139) R^(D139) R^(D139) L_(C140) R^(D140) R^(D140)L_(C141) R^(D141) R^(D141) L_(C142) R^(D142) R^(D142) L_(C143) R^(D143)R^(D143) L_(C144) R^(D144) R^(D144) L_(C145) R^(D145) R^(D145) L_(C146)R^(D146) R^(D146) L_(C147) R^(D147) R^(D147) L_(C148) R^(D148) R^(D148)L_(C149) R^(D149) R^(D149) L_(C150) R^(D150) R^(D150) L_(C151) R^(D151)R^(D151) L_(C152) R^(D152) R^(D152) L_(C153) R^(D153) R^(D153) L_(C154)R^(D154) R^(D154) L_(C155) R^(D155) R^(D155) L_(C156) R^(D156) R^(D156)L_(C157) R^(D157) R^(D157) L_(C158) R^(D158) R^(D158) L_(C159) R^(D159)R^(D159) L_(C160) R^(D160) R^(D160) L_(C161) R^(D161) R^(D161) L_(C162)R^(D162) R^(D162) L_(C163) R^(D163) R^(D163) L_(C164) R^(D164) R^(D164)L_(C165) R^(D165) R^(D165) L_(C166) R^(D166) R^(D166) L_(C167) R^(D167)R^(D167) L_(C168) R^(D168) R^(D168) L_(C169) R^(D169) R^(D169) L_(C170)R^(D170) R^(D170) L_(C171) R^(D171) R^(D171) L_(C172) R^(D172) R^(D172)L_(C173) R^(D173) R^(D173) L_(C174) R^(D174) R^(D174) L_(C175) R^(D175)R^(D175) L_(C176) R^(D176) R^(D176) L_(C177) R^(D177) R^(D177) L_(C178)R^(D178) R^(D178) L_(C179) R^(D179) R^(D179) L_(C180) R^(D180) R^(D180)L_(C181) R^(D181) R^(D181) L_(C182) R^(D182) R^(D182) L_(C183) R^(D183)R^(D183) L_(C184) R^(D184) R^(D184) L_(C185) R^(D185) R^(D185) L_(C186)R^(D186) R^(D186) L_(C187) R^(D187) R^(D187) L_(C188) R^(D188) R^(D188)L_(C189) R^(D189) R^(D189) L_(C190) R^(D190) R^(D190) L_(C191) R^(D191)R^(D191) L_(C192) R^(D192) R^(D192) L_(C193) R^(D1) R^(D3) L_(C194)R^(D1) R^(D4) L_(C195) R^(D1) R^(D5) L_(C196) R^(D1) R^(D9) L_(C197)R^(D1) R^(D10) L_(C198) R^(D1) R^(D17) L_(C199) R^(D1) R^(D18) L_(C200)R^(D1) R^(D20) L_(C201) R^(D1) R^(D22) L_(C202) R^(D1) R^(D37) L_(C203)R^(D1) R^(D40) L_(C204) R^(D1) R^(D41) L_(C205) R^(D1) R^(D42) L_(C206)R^(D1) R^(D43) L_(C207) R^(D1) R^(D48) L_(C208) R^(D1) R^(D49) L_(C209)R^(D1) R^(D50) L_(C210) R^(D1) R^(D54) L_(C211) R^(D1) R^(D55) L_(C212)R^(D1) R^(D58) L_(C213) R^(D1) R^(D59) L_(C214) R^(D1) R^(D78) L_(C215)R^(D1) R^(D79) L_(C216) R^(D1) R^(D81) L_(C217) R^(D1) R^(D87) L_(C218)R^(D1) R^(D88) L_(C219) R^(D1) R^(D89) L_(C220) R^(D1) R^(D93) L_(C221)R^(D1) R^(D116) L_(C222) R^(D1) R^(D117) L_(C223) R^(D1) R^(D118)L_(C224) R^(D1) R^(D119) L_(C225) R^(D1) R^(D120) L_(C226) R^(D1)R^(D133) L_(C227) R^(D1) R^(D134) L_(C228) R^(D1) R^(D135) L_(C229)R^(D1) R^(D136) L_(C230) R^(D1) R^(D143) L_(C231) R^(D1) R^(D144)L_(C232) R^(D1) R^(D145) L_(C233) R^(D1) R^(D146) L_(C234) R^(D1)R^(D147) L_(C235) R^(D1) R^(D149) L_(C236) R^(D1) R^(D151) L_(C237)R^(D1) R^(D154) L_(C238) R^(D1) R^(D155) L_(C239) R^(D1) R^(D161)L_(C240) R^(D1) R^(D175) L_(C241) R^(D4) R^(D3) L_(C242) R^(D4) R^(D5)L_(C243) R^(D4) R^(D9) L_(C244) R^(D4) R^(D10) L_(C245) R^(D4) R^(D17)L_(C246) R^(D4) R^(D18) L_(C247) R^(D4) R^(D20) L_(C248) R^(D4) R^(D22)L_(C249) R^(D4) R^(D37) L_(C250) R^(D4) R^(D40) L_(C251) R^(D4) R^(D41)L_(C252) R^(D4) R^(D42) L_(C253) R^(D4) R^(D43) L_(C254) R^(D4) R^(D48)L_(C255) R^(D4) R^(D49) L_(C256) R^(D4) R^(D50) L_(C257) R^(D4) R^(D54)L_(C258) R^(D4) R^(D55) L_(C259) R^(D4) R^(D58) L_(C260) R^(D4) R^(D59)L_(C261) R^(D4) R^(D78) L_(C262) R^(D4) R^(D79) L_(C263) R^(D4) R^(D81)L_(C264) R^(D4) R^(D87) L_(C265) R^(D4) R^(D88) L_(C266) R^(D4) R^(D89)L_(C267) R^(D4) R^(D93) L_(C268) R^(D4) R^(D116) L_(C269) R^(D4)R^(D117) L_(C270) R^(D4) R^(D118) L_(C271) R^(D4) R^(D119) L_(C272)R^(D4) R^(D120) L_(C273) R^(D4) R^(D133) L_(C274) R^(D4) R^(D134)L_(C275) R^(D4) R^(D135) L_(C276) R^(D4) R^(D136) L_(C277) R^(D4)R^(D143) L_(C278) R^(D4) R^(D144) L_(C279) R^(D4) R^(D145) L_(C280)R^(D4) R^(D146) L_(C281) R^(D4) R^(D147) L_(C282) R^(D4) R^(D149)L_(C283) R^(D4) R^(D151) L_(C284) R^(D4) R^(D154) L_(C285) R^(D4)R^(D155) L_(C286) R^(D4) R^(D161) L_(C287) R^(D4) R^(D175) L_(C288)R^(D9) R^(D3) L_(C289) R^(D9) R^(D5) L_(C290) R^(D9) R^(D10) L_(C291)R^(D9) R^(D17) L_(C292) R^(D9) R^(D18) L_(C293) R^(D9) R^(D20) L_(C294)R^(D9) R^(D22) L_(C295) R^(D9) R^(D37) L_(C296) R^(D9) R^(D40) L_(C297)R^(D9) R^(D41) L_(C298) R^(D9) R^(D42) L_(C299) R^(D9) R^(D43) L_(C300)R^(D9) R^(D48) L_(C301) R^(D9) R^(D49) L_(C302) R^(D9) R^(D50) L_(C303)R^(D9) R^(D54) L_(C304) R^(D9) R^(D55) L_(C305) R^(D9) R^(D58) L_(C306)R^(D9) R^(D59) L_(C307) R^(D9) R^(D78) L_(C308) R^(D9) R^(D79) L_(C309)R^(D9) R^(D81) L_(C310) R^(D9) R^(D87) L_(C311) R^(D9) R^(D88) L_(C312)R^(D9) R^(D89) L_(C313) R^(D9) R^(D93) L_(C314) R^(D9) R^(D116) L_(C315)R^(D9) R^(D117) L_(C316) R^(D9) R^(D118) L_(C317) R^(D9) R^(D119)L_(C318) R^(D9) R^(D120) L_(C319) R^(D9) R^(D133) L_(C320) R^(D9)R^(D134) L_(C321) R^(D9) R^(D135) L_(C322) R^(D9) R^(D136) L_(C323)R^(D9) R^(D143) L_(C324) R^(D9) R^(D144) L_(C325) R^(D9) R^(D145)L_(C326) R^(D9) R^(D146) L_(C327) R^(D9) R^(D147) L_(C328) R^(D9)R^(D149) L_(C329) R^(D9) R^(D151) L_(C330) R^(D9) R^(D154) L_(C331)R^(D9) R^(D155) L_(C332) R^(D9) R^(D161) L_(C333) R^(D9) R^(D175)L_(C334) R^(D10) R^(D3) L_(C335) R^(D10) R^(D5) L_(C336) R^(D10) R^(D17)L_(C337) R^(D10) R^(D18) L_(C338) R^(D10) R^(D20) L_(C339) R^(D10)R^(D22) L_(C340) R^(D10) R^(D37) L_(C341) R^(D10) R^(D40) L_(C342)R^(D10) R^(D41) L_(C343) R^(D10) R^(D42) L_(C344) R^(D10) R^(D43)L_(C345) R^(D10) R^(D48) L_(C346) R^(D10) R^(D49) L_(C347) R^(D10)R^(D50) L_(C348) R^(D10) R^(D54) L_(C349) R^(D10) R^(D55) L_(C350)R^(D10) R^(D58) L_(C351) R^(D10) R^(D59) L_(C352) R^(D10) R^(D78)L_(C353) R^(D10) R^(D79) L_(C354) R^(D10) R^(D81) L_(C355) R^(D10)R^(D87) L_(C356) R^(D10) R^(D88) L_(C357) R^(D10) R^(D89) L_(C358)R^(D10) R^(D93) L_(C359) R^(D10) R^(D116) L_(C360) R^(D10) R^(D117)L_(C361) R^(D10) R^(D118) L_(C362) R^(D10) R^(D119) L_(C363) R^(D10)R^(D120) L_(C364) R^(D10) R^(D133) L_(C365) R^(D10) R^(D14) L_(C366)R^(D10) R^(D135) L_(C367) R^(D10) R^(D136) L_(C368) R^(D10) R^(D143)L_(C369) R^(D10) R^(D144) L_(C370) R^(D10) R^(D145) L_(C371) R^(D10)R^(D146) L_(C372) R^(D10) R^(D147) L_(C373) R^(D10) R^(D149) L_(C374)R^(D10) R^(D151) L_(C375) R^(D10) R^(D154) L_(C376) R^(D10) R^(D155)L_(C377) R^(D10) R^(D161) L_(C378) R^(D10) R^(D175) L_(C379) R^(D17)R^(D3) L_(C380) R^(D17) R^(D5) L_(C381) R^(D17) R^(D18) L_(C382) R^(D17)R^(D20) L_(C383) R^(D17) R^(D22) L_(C384) R^(D17) R^(D37) L_(C385)R^(D17) R^(D40) L_(C386) R^(D17) R^(D41) L_(C387) R^(D17) R^(D42)L_(C388) R^(D17) R^(D43) L_(C389) R^(D17) R^(D48) L_(C390) R^(D17)R^(D49) L_(C391) R^(D17) R^(D50) L_(C392) R^(D17) R^(D54) L_(C393)R^(D17) R^(D55) L_(C394) R^(D17) R^(D58) L_(C395) R^(D17) R^(D59)L_(C396) R^(D17) R^(D78) L_(C397) R^(D17) R^(D79) L_(C398) R^(D17)R^(D81) L_(C399) R^(D17) R^(D87) L_(C400) R^(D17) R^(D88) L_(C401)R^(D17) R^(D89) L_(C402) R^(D17) R^(D93) L_(C403) R^(D17) R^(D116)L_(C404) R^(D17) R^(D117) L_(C405) R^(D17) R^(D118) L_(C406) R^(D17)R^(D119) L_(C407) R^(D17) R^(D120) L_(C408) R^(D17) R^(D133) L_(C409)R^(D17) R^(D134) L_(C410) R^(D17) R^(D135) L_(C411) R^(D17) R^(D136)L_(C412) R^(D17) R^(D143) L_(C413) R^(D17) R^(D144) L_(C414) R^(D17)R^(D145) L_(C415) R^(D17) R^(D146) L_(C416) R^(D17) R^(D147) L_(C417)R^(D17) R^(D149) L_(C418) R^(D17) R^(D151) L_(C419) R^(D17) R^(D154)L_(C420) R^(D17) R^(D155) L_(C421) R^(D17) R^(D161) L_(C422) R^(D17)R^(D175) L_(C423) R^(D50) R^(D3) L_(C424) R^(D50) R^(D5) L_(C425)R^(D50) R^(D18) L_(C426) R^(D50) R^(D20) L_(C427) R^(D50) R^(D22)L_(C428) R^(D50) R^(D37) L_(C429) R^(D50) R^(D40) L_(C430) R^(D50)R^(D41) L_(C431) R^(D50) R^(D42) L_(C432) R^(D50) R^(D43) L_(C433)R^(D50) R^(D48) L_(C434) R^(D50) R^(D49) L_(C435) R^(D50) R^(D54)L_(C436) R^(D50) R^(D55) L_(C437) R^(D50) R^(D58) L_(C438) R^(D50)R^(D59) L_(C439) R^(D50) R^(D78) L_(C440) R^(D50) R^(D79) L_(C441)R^(D50) R^(D81) L_(C442) R^(D50) R^(D87) L_(C443) R^(D50) R^(D88)L_(C444) R^(D50) R^(D89) L_(C445) R^(D50) R^(D93) L_(C446) R^(D50)R^(D116) L_(C447) R^(D50) R^(D117) L_(C448) R^(D50) R^(D118) L_(C449)R^(D50) R^(D119) L_(C450) R^(D50) R^(D120) L_(C451) R^(D50) R^(D133)L_(C452) R^(D50) R^(D134) L_(C453) R^(D50) R^(D135) L_(C454) R^(D50)R^(D136) L_(C455) R^(D50) R^(D143) L_(C456) R^(D50) R^(D144) L_(C457)R^(D50) R^(D145) L_(C458) R^(D50) R^(D146) L_(C459) R^(D50) R^(D147)L_(C460) R^(D50) R^(D149) L_(C461) R^(D50) R^(D151) L_(C462) R^(D50)R^(D154) L_(C463) R^(D50) R^(D155) L_(C464) R^(D50) R^(D161) L_(C465)R^(D50) R^(D175) L_(C466) R^(D55) R^(D3) L_(C467) R^(D55) R^(D5)L_(C468) R^(D55) R^(D18) L_(C469) R^(D55) R^(D20) L_(C470) R^(D55)R^(D22) L_(C471) R^(D55) R^(D37) L_(C472) R^(D55) R^(D40) L_(C473)R^(D55) R^(D41) L_(C474) R^(D55) R^(D42) L_(C475) R^(D55) R^(D42)L_(C476) R^(D55) R^(D48) L_(C477) R^(D55) R^(D49) L_(C478) R^(D55)R^(D54) L_(C479) R^(D55) R^(D58) L_(C480) R^(D55) R^(D59) L_(C481)R^(D55) R^(D78) L_(C482) R^(D55) R^(D79) L_(C483) R^(D55) R^(D81)L_(C484) R^(D55) R^(D87) L_(C485) R^(D55) R^(D88) L_(C486) R^(D55)R^(D89) L_(C487) R^(D55) R^(D93) L_(C488) R^(D55) R^(D116) L_(C489)R^(D55) R^(D117) L_(C490) R^(D55) R^(D118) L_(C491) R^(D55) R^(D119)L_(C492) R^(D55) R^(D120) L_(C493) R^(D55) R^(D133) L_(C494) R^(D55)R^(D134) L_(C495) R^(D55) R^(D135) L_(C496) R^(D55) R^(D136) L_(C497)R^(D55) R^(D143) L_(C498) R^(D55) R^(D144) L_(C499) R^(D55) R^(D145)L_(C500) R^(D55) R^(D146) L_(C501) R^(D55) R^(D147) L_(C502) R^(D55)R^(D149) L_(C503) R^(D55) R^(D151) L_(C504) R^(D55) R^(D154) L_(C505)R^(D55) R^(D155) L_(C506) R^(D55) R^(D161) L_(C507) R^(D55) R^(D175)L_(C508) R^(D116) R^(D3) L_(C509) R^(D116) R^(D5) L_(C510) R^(D116)R^(D17) L_(C511) R^(D116) R^(D18) L_(C512) R^(D116) R^(D20) L_(C513)R^(D116) R^(D22) L_(C514) R^(D116) R^(D37) L_(C515) R^(D116) R^(D40)L_(C516) R^(D116) R^(D41) L_(C517) R^(D116) R^(D42) L_(C518) R^(D116)R^(D43) L_(C519) R^(D116) R^(D48) L_(C520) R^(D116) R^(D49) L_(C521)R^(D116) R^(D54) L_(C522) R^(D116) R^(D58) L_(C523) R^(D116) R^(D59)L_(C524) R^(D116) R^(D78) L_(C525) R^(D116) R^(D79) L_(C526) R^(D116)R^(D81) L_(C527) R^(D116) R^(D87) L_(C528) R^(D116) R^(D88) L_(C529)R^(D116) R^(D89) L_(C530) R^(D116) R^(D93) L_(C531) R^(D116) R^(D117)L_(C532) R^(D116) R^(D118) L_(C533) R^(D116) R^(D119) L_(C534) R^(D116)R^(D120) L_(C535) R^(D116) R^(D133) L_(C536) R^(D116) R^(D134) L_(C537)R^(D116) R^(D135) L_(C538) R^(D116) R^(D136) L_(C539) R^(D116) R^(D143)L_(C540) R^(D116) R^(D144) L_(C541) R^(D116) R^(D145) L_(C542) R^(D116)R^(D146) L_(C543) R^(D116) R^(D147) L_(C544) R^(D116) R^(D149) L_(C545)R^(D116) R^(D151) L_(C546) R^(D116) R^(D154) L_(C547) R^(D116) R^(D155)L_(C548) R^(D116) R^(D161) L_(C549) R^(D116) R^(D175) L_(C550) R^(D143)R^(D3) L_(C551) R^(D143) R^(D5) L_(C552) R^(D143) R^(D17) L_(C553)R^(D143) R^(D18) L_(C554) R^(D143) R^(D20) L_(C555) R^(D143) R^(D22)L_(C556) R^(D143) R^(D37) L_(C557) R^(D143) R^(D40) L_(C558) R^(D143)R^(D41) L_(C559) R^(D143) R^(D42) L_(C560) R^(D143) R^(D43) L_(C561)R^(D143) R^(D48) L_(C562) R^(D143) R^(D49) L_(C563) R^(D143) R^(D54)L_(C564) R^(D143) R^(D58) L_(C565) R^(D143) R^(D59) L_(C566) R^(D143)R^(D78) L_(C567) R^(D143) R^(D79) L_(C568) R^(D143) R^(D81) L_(C569)R^(D143) R^(D87) L_(C570) R^(D143) R^(D88) L_(C571) R^(D143) R^(D89)L_(C572) R^(D143) R^(D93) L_(C573) R^(D143) R^(D116) L_(C574) R^(D143)R^(D117) L_(C575) R^(D143) R^(D118) L_(C576) R^(D143) R^(D119) L_(C577)R^(D143) R^(D120) L_(C578) R^(D143) R^(D133) L_(C579) R^(D143) R^(D134)L_(C580) R^(D143) R^(D135) L_(C581) R^(D143) R^(D136) L_(C582) R^(D143)R^(D144) L_(C583) R^(D143) R^(D145) L_(C584) R^(D143) R^(D146) L_(C585)R^(D143) R^(D147) L_(C586) R^(D143) R^(D149) L_(C587) R^(D143) R^(D151)L_(C588) R^(D143) R^(D154) L_(C589) R^(D143) R^(D155) L_(C590) R^(D143)R^(D161) L_(C591) R^(D143) R^(D175) L_(C592) R^(D144) R^(D3) L_(C593)R^(D144) R^(D5) L_(C594) R^(D144) R^(D17) L_(C595) R^(D144) R^(D18)L_(C596) R^(D144) R^(D20) L_(C597) R^(D144) R^(D22) L_(C598) R^(D144)R^(D37) L_(C599) R^(D144) R^(D40) L_(C600) R^(D144) R^(D41) L_(C601)R^(D144) R^(D42) L_(C602) R^(D144) R^(D43) L_(C603) R^(D144) R^(D48)L_(C604) R^(D144) R^(D49) L_(C605) R^(D144) R^(D54) L_(C606) R^(D144)R^(D58) L_(C607) R^(D144) R^(D59) L_(C608) R^(D144) R^(D78) L_(C609)R^(D144) R^(D79) L_(C610) R^(D144) R^(D81) L_(C611) R^(D144) R^(D87)L_(C612) R^(D144) R^(D88) L_(C613) R^(D144) R^(D89) L_(C614) R^(D144)R^(D93) L_(C615) R^(D144) R^(D116) L_(C616) R^(D144) R^(D117) L_(C617)R^(D144) R^(D118) L_(C618) R^(D144) R^(D119) L_(C619) R^(D144) R^(D120)L_(C620) R^(D144) R^(D133) L_(C621) R^(D144) R^(D134) L_(C622) R^(D144)R^(D135) L_(C623) R^(D144) R^(D136) L_(C624) R^(D144) R^(D145) L_(C625)R^(D144) R^(D146) L_(C626) R^(D144) R^(D147) L_(C627) R^(D144) R^(D149)L_(C628) R^(D144) R^(D151) L_(C629) R^(D144) R^(D154) L_(C630) R^(D144)R^(D155) L_(C631) R^(D144) R^(D161) L_(C632) R^(D144) R^(D175) L_(C633)R^(D145) R^(D3) L_(C634) R^(D145) R^(D5) L_(C635) R^(D145) R^(D17)L_(C636) R^(D145) R^(D18) L_(C637) R^(D145) R^(D20) L_(C638) R^(D145)R^(D22) L_(C639) R^(D145) R^(D37) L_(C640) R^(D145) R^(D40) L_(C641)R^(D145) R^(D41) L_(C642) R^(D145) R^(D42) L_(C643) R^(D145) R^(D43)L_(C644) R^(D145) R^(D48) L_(C645) R^(D145) R^(D49) L_(C646) R^(D145)R^(D54) L_(C647) R^(D145) R^(D58) L_(C648) R^(D145) R^(D59) L_(C649)R^(D145) R^(D78) L_(C650) R^(D145) R^(D79) L_(C651) R^(D145) R^(D81)L_(C652) R^(D145) R^(D87) L_(C653) R^(D145) R^(D88) L_(C654) R^(D145)R^(D89) L_(C655) R^(D145) R^(D93) L_(C656) R^(D145) R^(D116) L_(C657)R^(D145) R^(D117) L_(C658) R^(D145) R^(D118) L_(C659) R^(D145) R^(D119)L_(C660) R^(D145) R^(D120) L_(C661) R^(D145) R^(D133) L_(C662) R^(D145)R^(D134) L_(C663) R^(D145) R^(D135) L_(C664) R^(D145) R^(D136) L_(C665)R^(D145) R^(D146) L_(C666) R^(D145) R^(D147) L_(C667) R^(D145) R^(D149)L_(C668) R^(D145) R^(D151) L_(C669) R^(D145) R^(D154) L_(C670) R^(D145)R^(D155) L_(C671) R^(D145) R^(D161) L_(C672) R^(D145) R^(D175) L_(C673)R^(D146) R^(D3) L_(C674) R^(D146) R^(D5) L_(C675) R^(D146) R^(D17)L_(C676) R^(D146) R^(D18) L_(C677) R^(D146) R^(D20) L_(C678) R^(D146)R^(D22) L_(C679) R^(D146) R^(D37) L_(C680) R^(D146) R^(D40) L_(C681)R^(D146) R^(D41) L_(C682) R^(D146) R^(D42) L_(C683) R^(D146) R^(D43)L_(C684) R^(D146) R^(D48) L_(C685) R^(D146) R^(D49) L_(C686) R^(D146)R^(D54) L_(C687) R^(D146) R^(D58) L_(C688) R^(D146) R^(D59) L_(C689)R^(D146) R^(D78) L_(C690) R^(D146) R^(D79) L_(C691) R^(D146) R^(D81)L_(C692) R^(D146) R^(D87) L_(C693) R^(D146) R^(D88) L_(C694) R^(D146)R^(D89) L_(C695) R^(D146) R^(D93) L_(C696) R^(D146) R^(D117) L_(C697)R^(D146) R^(D118) L_(C698) R^(D146) R^(D119) L_(C699) R^(D146) R^(D120)L_(C700) R^(D146) R^(D133) L_(C701) R^(D146) R^(D134) L_(C702) R^(D146)R^(D135) L_(C703) R^(D146) R^(D136) L_(C704) R^(D146) R^(D146) L_(C705)R^(D146) R^(D147) L_(C706) R^(D146) R^(D149) L_(C707) R^(D146) R^(D151)L_(C708) R^(D146) R^(D154) L_(C709) R^(D146) R^(D155) L_(C710) R^(D146)R^(D161) L_(C711) R^(D146) R^(D175) L_(C712) R^(D133) R^(D3) L_(C713)R^(D133) R^(D5) L_(C714) R^(D133) R^(D3) L_(C715) R^(D133) R^(D18)L_(C716) R^(D133) R^(D20) L_(C717) R^(D133) R^(D22) L_(C718) R^(D133)R^(D37) L_(C719) R^(D133) R^(D40) L_(C720) R^(D133) R^(D41) L_(C721)R^(D133) R^(D42) L_(C722) R^(D133) R^(D43) L_(C723) R^(D133) R^(D48)L_(C724) R^(D133) R^(D49) L_(C725) R^(D133) R^(D54) L_(C726) R^(D133)R^(D58) L_(C727) R^(D133) R^(D59) L_(C728) R^(D133) R^(D78) L_(C729)R^(D133) R^(D79) L_(C730) R^(D133) R^(D81) L_(C731) R^(D133) R^(D87)L_(C732) R^(D133) R^(D88) L_(C733) R^(D133) R^(D89) L_(C734) R^(D133)R^(D93) L_(C735) R^(D133) R^(D117) L_(C736) R^(D133) R^(D118) L_(C737)R^(D133) R^(D119) L_(C738) R^(D133) R^(D120) L_(C739) R^(D133) R^(D133)L_(C740) R^(D133) R^(D134) L_(C741) R^(D133) R^(D135) L_(C742) R^(D133)R^(D136) L_(C743) R^(D133) R^(D146) L_(C744) R^(D133) R^(D147) L_(C745)R^(D133) R^(D149) L_(C746) R^(D133) R^(D151) L_(C747) R^(D133) R^(D154)L_(C748) R^(D133) R^(D155) L_(C749) R^(D133) R^(D161) L_(C750) R^(D133)R^(D175) L_(C751) R^(D175) R^(D3) L_(C752) R^(D175) R^(D5) L_(C753)R^(D175) R^(D18) L_(C754) R^(D175) R^(D20) L_(C755) R^(D175) R^(D22)L_(C756) R^(D175) R^(D37) L_(C757) R^(D175) R^(D40) L_(C758) R^(D175)R^(D41) L_(C759) R^(D175) R^(D42) L_(C760) R^(D175) R^(D43) L_(C761)R^(D175) R^(D48) L_(C762) R^(D175) R^(D49) L_(C763) R^(D175) R^(D54)L_(C764) R^(D175) R^(D58) L_(C765) R^(D175) R^(D59) L_(C766) R^(D175)R^(D78) L_(C767) R^(D175) R^(D79) L_(C768) R^(D175) R^(D81) L_(C769)R^(D193) R^(D193) L_(C770) R^(D194) R^(D194) L_(C771) R^(D195) R^(D195)L_(C772) R^(D196) R^(D196) L_(C773) R^(D197) R^(D197) L_(C774) R^(D198)R^(D198) L_(C775) R^(D199) R^(D199) L_(C776) R^(D200) R^(D200) L_(C777)R^(D201) R^(D201) L_(C778) R^(D202) R^(D202) L_(C779) R^(D203) R^(D203)L_(C780) R^(D204) R^(D204) L_(C781) R^(D205) R^(D205) L_(C782) R^(D206)R^(D206) L_(C783) R^(D207) R^(D207) L_(C784) R^(D208) R^(D208) L_(C785)R^(D209) R^(D209) L_(C786) R^(D210) R^(D210) L_(C787) R^(D211) R^(D211)L_(C788) R^(D212) R^(D212) L_(C789) R^(D213) R^(D213) L_(C790) R^(D214)R^(D214) L_(C791) R^(D215) R^(D215) L_(C792) R^(D216) R^(D216) L_(C793)R^(D217) R^(D217) L_(C794) R^(D218) R^(D218) L_(C795) R^(D219) R^(D219)L_(C796) R^(D220) R^(D220) L_(C797) R^(D221) R^(D221) L_(C798) R^(D222)R^(D222) L_(C799) R^(D223) R^(D223) L_(C800) R^(D224) R^(D224) L_(C801)R^(D225) R^(D225) L_(C802) R^(D226) R^(D226) L_(C803) R^(D227) R^(D227)L_(C804) R^(D228) R^(D228) L_(C805) R^(D229) R^(D229) L_(C806) R^(D230)R^(D230) L_(C807) R^(D231) R^(D231) L_(C808) R^(D232) R^(D232) L_(C809)R^(D233) R^(D233) L_(C810) R^(D234) R^(D234) L_(C811) R^(D235) R^(D235)L_(C812) R^(D236) R^(D236) L_(C813) R^(D237) R^(D237) L_(C814) R^(D238)R^(D238) L_(C815) R^(D239) R^(D239) L_(C816) R^(D240) R^(D240) L_(C817)R^(D241) R^(D241) L_(C818) R^(D242) R^(D242) L_(C819) R^(D243) R^(D243)L_(C820) R^(D244) R^(D244) L_(C821) R^(D245) R^(D245) L_(C822) R^(D246)R^(D246) L_(C823) R^(D17) R^(D193) L_(C824) R^(D17) R^(D194) L_(C825)R^(D17) R^(D195) L_(C826) R^(D17) R^(D196) L_(C827) R^(D17) R^(D197)L_(C828) R^(D17) R^(D198) L_(C829) R^(D17) R^(D199) L_(C830) R^(D17)R^(D200) L_(C831) R^(D17) R^(D201) L_(C832) R^(D17) R^(D202) L_(C833)R^(D17) R^(D203) L_(C834) R^(D17) R^(D204) L_(C835) R^(D17) R^(D205)L_(C836) R^(D17) R^(D206) L_(C837) R^(D17) R^(D207) L_(C838) R^(D17)R^(D208) L_(C839) R^(D17) R^(D209) L_(C840) R^(D17) R^(D210) L_(C841)R^(D17) R^(D211) L_(C842) R^(D17) R^(D212) L_(C843) R^(D17) R^(D213)L_(C844) R^(D17) R^(D214) L_(C845) R^(D17) R^(D215) L_(C846) R^(D17)R^(D216) L_(C847) R^(D17) R^(D217) L_(C848) R^(D17) R^(D218) L_(C849)R^(D17) R^(D219) L_(C850) R^(D17) R^(D220) L_(C851) R^(D17) R^(D221)L_(C852) R^(D17) R^(D222) L_(C853) R^(D17) R^(D223) L_(C854) R^(D17)R^(D224) L_(C855) R^(D17) R^(D225) L_(C856) R^(D17) R^(D226) L_(C857)R^(D17) R^(D227) L_(C858) R^(D17) R^(D228) L_(C859) R^(D17) R^(D229)L_(C860) R^(D17) R^(D230) L_(C861) R^(D17) R^(D231) L_(C862) R^(D17)R^(D232) L_(C863) R^(D17) R^(D233) L_(C864) R^(D17) R^(D234) L_(C865)R^(D17) R^(D235) L_(C866) R^(D17) R^(D236) L_(C867) R^(D17) R^(D237)L_(C868) R^(D17) R^(D238) L_(C869) R^(D17) R^(D239) L_(C870) R^(D17)R^(D240) L_(C871) R^(D17) R^(D241) L_(C872) R^(D17) R^(D242) L_(C873)R^(D17) R^(D243) L_(C874) R^(D17) R^(D244) L_(C875) R^(D17) R^(D245)L_(C876) R^(D17) R^(D246) L_(C877) R^(D1) R^(D193) L_(C878) R^(D1)R^(D194) L_(C879) R^(D1) R^(D195) L_(C880) R^(D1) R^(D196) L_(C881)R^(D1) R^(D197) L_(C882) R^(D1) R^(D198) L_(C883) R^(D1) R^(D199)L_(C884) R^(D1) R^(D200) L_(C885) R^(D1) R^(D201) L_(C886) R^(D1)R^(D202) L_(C887) R^(D1) R^(D203) L_(C888) R^(D1) R^(D204) L_(C889)R^(D1) R^(D205) L_(C890) R^(D1) R^(D206) L_(C891) R^(D1) R^(D207)L_(C892) R^(D1) R^(D208) L_(C893) R^(D1) R^(D209) L_(C894) R^(D1)R^(D210) L_(C895) R^(D1) R^(D211) L_(C896) R^(D1) R^(D212) L_(C897)R^(D1) R^(D213) L_(C898) R^(D1) R^(D214) L_(C899) R^(D1) R^(D215)L_(C900) R^(D1) R^(D216) L_(C901) R^(D1) R^(D217) L_(C902) R^(D1)R^(D218) L_(C903) R^(D1) R^(D219) L_(C904) R^(D1) R^(D220) L_(C905)R^(D1) R^(D221) L_(C906) R^(D1) R^(D222) L_(C907) R^(D1) R^(D223)L_(C908) R^(D1) R^(D224) L_(C909) R^(D1) R^(D225) L_(C910) R^(D1)R^(D226) L_(C911) R^(D1) R^(D227) L_(C912) R^(D1) R^(D228) L_(C913)R^(D1) R^(D229) L_(C914) R^(D1) R^(D230) L_(C915) R^(D1) R^(D231)L_(C916) R^(D1) R^(D232) L_(C917) R^(D1) R^(D233) L_(C918) R^(D1)R^(D234) L_(C919) R^(D1) R^(D235) L_(C920) R^(D1) R^(D236) L_(C921)R^(D1) R^(D237) L_(C922) R^(D1) R^(D238) L_(C923) R^(D1) R^(D239)L_(C924) R^(D1) R^(D240) L_(C925) R^(D1) R^(D241) L_(C926) R^(D1)R^(D242) L_(C927) R^(D1) R^(D243) L_(C928) R^(D1) R^(D244) L_(C929)R^(D1) R^(D245) L_(C930) R^(D1) R^(D246) L_(C931) R^(D50) R^(D193)L_(C932) R^(D50) R^(D194) L_(C933) R^(D50) R^(D195) L_(C934) R^(D50)R^(D196) L_(C935) R^(D50) R^(D197) L_(C936) R^(D50) R^(D198) L_(C937)R^(D50) R^(D199) L_(C938) R^(D50) R^(D200) L_(C939) R^(D50) R^(D201)L_(C940) R^(D50) R^(D202) L_(C941) R^(D50) R^(D203) L_(C942) R^(D50)R^(D204) L_(C943) R^(D50) R^(D205) L_(C944) R^(D50) R^(D206) L_(C945)R^(D50) R^(D207) L_(C946) R^(D50) R^(D208) L_(C947) R^(D50) R^(D209)L_(C948) R^(D50) R^(D210) L_(C949) R^(D50) R^(D211) L_(C950) R^(D50)R^(D212) L_(C951) R^(D50) R^(D213) L_(C952) R^(D50) R^(D214) L_(C953)R^(D50) R^(D215) L_(C954) R^(D50) R^(D216) L_(C955) R^(D50) R^(D217)L_(C956) R^(D50) R^(D218) L_(C957) R^(D50) R^(D219) L_(C958) R^(D50)R^(D220) L_(C959) R^(D50) R^(D221) L_(C960) R^(D50) R^(D222) L_(C961)R^(D50) R^(D223) L_(C962) R^(D50) R^(D224) L_(C963) R^(D50) R^(D225)L_(C964) R^(D50) R^(D226) L_(C965) R^(D50) R^(D227) L_(C966) R^(D50)R^(D228) L_(C967) R^(D50) R^(D229) L_(C968) R^(D50) R^(D230) L_(C969)R^(D50) R^(D231) L_(C970) R^(D50) R^(D232) L_(C971) R^(D50) R^(D233)L_(C972) R^(D50) R^(D234) L_(C973) R^(D50) R^(D235) L_(C974) R^(D50)R^(D236) L_(C975) R^(D50) R^(D237) L_(C976) R^(D50) R^(D238) L_(C977)R^(D50) R^(D239) L_(C978) R^(D50) R^(D240) L_(C979) R^(D50) R^(D241)L_(C980) R^(D50) R^(D242) L_(C981) R^(D50) R^(D243) L_(C982) R^(D50)R^(D244) L_(C983) R^(D50) R^(D245) L_(C984) R^(D50) R^(D246) L_(C985)R^(D4) R^(D193) L_(C986) R^(D4) R^(D194) L_(C987) R^(D4) R^(D195)L_(C988) R^(D4) R^(D196) L_(C989) R^(D4) R^(D197) L_(C990) R^(D4)R^(D198) L_(C991) R^(D4) R^(D199) L_(C992) R^(D4) R^(D200) L_(C993)R^(D4) R^(D201) L_(C994) R^(D4) R^(D202) L_(C995) R^(D4) R^(D203)L_(C996) R^(D4) R^(D204) L_(C997) R^(D4) R^(D205) L_(C998) R^(D4)R^(D206) L_(C999) R^(D4) R^(D207) L_(C1000) R^(D4) R^(D208) L_(C1001)R^(D4) R^(D209) L_(C1002) R^(D4) R^(D210) L_(C1003) R^(D4) R^(D211)L_(C1004) R^(D4) R^(D212) L_(C1005) R^(D4) R^(D213) L_(C1006) R^(D4)R^(D214) L_(C1007) R^(D4) R^(D215) L_(C1008) R^(D4) R^(D216) L_(C1009)R^(D4) R^(D217) L_(C1010) R^(D4) R^(D218) L_(C1011) R^(D4) R^(D219)L_(C1012) R^(D4) R^(D220) L_(C1013) R^(D4) R^(D221) L_(C1014) R^(D4)R^(D222) L_(C1015) R^(D4) R^(D223) L_(C1016) R^(D4) R^(D224) L_(C1017)R^(D4) R^(D225) L_(C1018) R^(D4) R^(D226) L_(C1019) R^(D4) R^(D227)L_(C1020) R^(D4) R^(D228) L_(C1021) R^(D4) R^(D229) L_(C1022) R^(D4)R^(D230) L_(C1023) R^(D4) R^(D231) L_(C1024) R^(D4) R^(D232) L_(C1025)R^(D4) R^(D233) L_(C1026) R^(D4) R^(D234) L_(C1027) R^(D4) R^(D235)L_(C1028) R^(D4) R^(D236) L_(C1029) R^(D4) R^(D237) L_(C1030) R^(D4)R^(D238) L_(C1031) R^(D4) R^(D239) L_(C1032) R^(D4) R^(D240) L_(C1033)R^(D4) R^(D241) L_(C1034) R^(D4) R^(D242) L_(C1035) R^(D4) R^(D243)L_(C1036) R^(D4) R^(D244) L_(C1037) R^(D4) R^(D245) L_(C1038) R^(D4)R^(D246) L_(C1039) R^(D145) R^(D193) L_(C1040) R^(D145) R^(D194)L_(C1041) R^(D145) R^(D195) L_(C1042) R^(D145) R^(D196) L_(C1043)R^(D145) R^(D197) L_(C1044) R^(D145) R^(D198) L_(C1045) R^(D145)R^(D199) L_(C1046) R^(D145) R^(D200) L_(C1047) R^(D145) R^(D201)L_(C1048) R^(D145) R^(D202) L_(C1049) R^(D145) R^(D203) L_(C1050)R^(D145) R^(D204) L_(C1051) R^(D145) R^(D205) L_(C1052) R^(D145)R^(D206) L_(C1053) R^(D145) R^(D207) L_(C1054) R^(D145) R^(D208)L_(C1055) R^(D145) R^(D209) L_(C1056) R^(D145) R^(D210) L_(C1057)R^(D145) R^(D211) L_(C1058) R^(D145) R^(D212) L_(C1059) R^(D145)R^(D213) L_(C1060) R^(D145) R^(D214) L_(C1061) R^(D145) R^(D215)L_(C1062) R^(D145) R^(D216) L_(C1063) R^(D145) R^(D217) L_(C1064)R^(D145) R^(D218) L_(C1065) R^(D145) R^(D219) L_(C1066) R^(D145)R^(D220) L_(C1067) R^(D145) R^(D221) L_(C1068) R^(D145) R^(D222)L_(C1069) R^(D145) R^(D223) L_(C1070) R^(D145) R^(D224) L_(C1071)R^(D145) R^(D225) L_(C1072) R^(D145) R^(D226) L_(C1073) R^(D145)R^(D227) L_(C1074) R^(D145) R^(D228) L_(C1075) R^(D145) R^(D229)L_(C1076) R^(D145) R^(D230) L_(C1077) R^(D145) R^(D231) L_(C1078)R^(D145) R^(D232) L_(C1079) R^(D145) R^(D233) L_(C1080) R^(D145)R^(D234) L_(C1081) R^(D145) R^(D235) L_(C1082) R^(D145) R^(D236)L_(C1083) R^(D145) R^(D237) L_(C1084) R^(D145) R^(D238) L_(C1085)R^(D145) R^(D239) L_(C1086) R^(D145) R^(D240) L_(C1087) R^(D145)R^(D241) L_(C1088) R^(D145) R^(D242) L_(C1089) R^(D145) R^(D243)L_(C1090) R^(D145) R^(D244) L_(C1091) R^(D145) R^(D245) L_(C1092)R^(D145) R^(D246) L_(C1093) R^(D9) R^(D193) L_(C1094) R^(D9) R^(D194)L_(C1095) R^(D9) R^(D195) L_(C1096) R^(D9) R^(D196) L_(C1097) R^(D9)R^(D197) L_(C1098) R^(D9) R^(D198) L_(C1099) R^(D9) R^(D199) L_(C1100)R^(D9) R^(D200) L_(C1101) R^(D9) R^(D201) L_(C1102) R^(D9) R^(D202)L_(C1103) R^(D9) R^(D203) L_(C1104) R^(D9) R^(D204) L_(C1105) R^(D9)R^(D205) L_(C1106) R^(D9) R^(D206) L_(C1107) R^(D9) R^(D207) L_(C1108)R^(D9) R^(D208) L_(C1109) R^(D9) R^(D209) L_(C1110) R^(D9) R^(D210)L_(C1111) R^(D9) R^(D211) L_(C1112) R^(D9) R^(D212) L_(C1113) R^(D9)R^(D213) L_(C1114) R^(D9) R^(D214) L_(C1115) R^(D9) R^(D215) L_(C1116)R^(D9) R^(D216) L_(C1117) R^(D9) R^(D217) L_(C1118) R^(D9) R^(D218)L_(C1119) R^(D9) R^(D219) L_(C1120) R^(D9) R^(D220) L_(C1121) R^(D9)R^(D221) L_(C1122) R^(D9) R^(D222) L_(C1123) R^(D9) R^(D223) L_(C1124)R^(D9) R^(D224) L_(C1125) R^(D9) R^(D225) L_(C1126) R^(D9) R^(D226)L_(C1127) R^(D9) R^(D227) L_(C1128) R^(D9) R^(D228) L_(C1129) R^(D9)R^(D229) L_(C1130) R^(D9) R^(D230) L_(C1131) R^(D9) R^(D231) L_(C1132)R^(D9) R^(D232) L_(C1133) R^(D9) R^(D233) L_(C1134) R^(D9) R^(D234)L_(C1135) R^(D9) R^(D235) L_(C1136) R^(D9) R^(D236) L_(C1137) R^(D9)R^(D237) L_(C1138) R^(D9) R^(D238) L_(C1139) R^(D9) R^(D239) L_(C1140)R^(D9) R^(D240) L_(C1141) R^(D9) R^(D241) L_(C1142) R^(D9) R^(D242)L_(C1143) R^(D9) R^(D243) L_(C1144) R^(D9) R^(D244) L_(C1145) R^(D9)R^(D245) L_(C1146) R^(D9) R^(D246) L_(C1147) R^(D168) R^(D193) L_(C1148)R^(D168) R^(D194) L_(C1149) R^(D168) R^(D195) L_(C1150) R^(D168)R^(D196) L_(C1151) R^(D168) R^(D197) L_(C1152) R^(D168) R^(D198)L_(C1153) R^(D168) R^(D199) L_(C1154) R^(D168) R^(D200) L_(C1155)R^(D168) R^(D201) L_(C1156) R^(D168) R^(D202) L_(C1157) R^(D168)R^(D203) L_(C1158) R^(D168) R^(D204) L_(C1159) R^(D168) R^(D205)L_(C1160) R^(D168) R^(D206) L_(C1161) R^(D168) R^(D207) L_(C1162)R^(D168) R^(D208) L_(C1163) R^(D168) R^(D209) L_(C1164) R^(D168)R^(D210) L_(C1165) R^(D168) R^(D211) L_(C1166) R^(D168) R^(D212)L_(C1167) R^(D168) R^(D213) L_(C1168) R^(D168) R^(D214) L_(C1169)R^(D168) R^(D215) L_(C1170) R^(D168) R^(D216) L_(C1171) R^(D168)R^(D217) L_(C1172) R^(D168) R^(D218) L_(C1173) R^(D168) R^(D219)L_(C1174) R^(D168) R^(D220) L_(C1175) R^(D168) R^(D221) L_(C1176)R^(D168) R^(D222) L_(C1177) R^(D168) R^(D223) L_(C1178) R^(D168)R^(D224) L_(C1179) R^(D168) R^(D225) L_(C1180) R^(D168) R^(D226)L_(C1181) R^(D168) R^(D227) L_(C1182) R^(D168) R^(D228) L_(C1183)R^(D168) R^(D229) L_(C1184) R^(D168) R^(D230) L_(C1185) R^(D168)R^(D231) L_(C1186) R^(D168) R^(D232) L_(C1187) R^(D168) R^(D233)L_(C1188) R^(D168) R^(D234) L_(C1189) R^(D168) R^(D235) L_(C1190)R^(D168) R^(D236) L_(C1191) R^(D168) R^(D237) L_(C1192) R^(D168)R^(D238) L_(C1193) R^(D168) R^(D239) L_(C1194) R^(D168) R^(D240)L_(C1195) R^(D168) R^(D241) L_(C1196) R^(D168) R^(D242) L_(C1197)R^(D168) R^(D243) L_(C1198) R^(D168) R^(D244) L_(C1199) R^(D168)R^(D245) L_(C1200) R^(D168) R^(D246) L_(C1201) R^(D10) R^(D193)L_(C1202) R^(D10) R^(D194) L_(C1203) R^(D10) R^(D195) L_(C1204) R^(D10)R^(D196) L_(C1205) R^(D10) R^(D197) L_(C1206) R^(D10) R^(D198) L_(C1207)R^(D10) R^(D199) L_(C1208) R^(D10) R^(D200) L_(C1209) R^(D10) R^(D201)L_(C1210) R^(D10) R^(D202) L_(C1211) R^(D10) R^(D203) L_(C1212) R^(D10)R^(D204) L_(C1213) R^(D10) R^(D205) L_(C1214) R^(D10) R^(D206) L_(C1215)R^(D10) R^(D207) L_(C1216) R^(D10) R^(D208) L_(C1217) R^(D10) R^(D209)L_(C1218) R^(D10) R^(D210) L_(C1219) R^(D10) R^(D211) L_(C1220) R^(D10)R^(D212) L_(C1221) R^(D10) R^(D213) L_(C1222) R^(D10) R^(D214) L_(C1223)R^(D10) R^(D215) L_(C1224) R^(D10) R^(D216) L_(C1225) R^(D10) R^(D217)L_(C1226) R^(D10) R^(D218) L_(C1227) R^(D10) R^(D219) L_(C1228) R^(D10)R^(D220) L_(C1229) R^(D10) R^(D221) L_(C1230) R^(D10) R^(D222) L_(C1231)R^(D10) R^(D223) L_(C1232) R^(D10) R^(D224) L_(C1233) R^(D10) R^(D225)L_(C1234) R^(D10) R^(D226) L_(C1235) R^(D10) R^(D227) L_(C1236) R^(D10)R^(D228) L_(C1237) R^(D10) R^(D229) L_(C1238) R^(D10) R^(D230) L_(C1239)R^(D10) R^(D231) L_(C1240) R^(D10) R^(D232) L_(C1241) R^(D10) R^(D233)L_(C1242) R^(D10) R^(D234) L_(C1243) R^(D10) R^(D235) L_(C1244) R^(D10)R^(D236) L_(C1245) R^(D10) R^(D237) L_(C1246) R^(D10) R^(D238) L_(C1247)R^(D10) R^(D239) L_(C1248) R^(D10) R^(D240) L_(C1249) R^(D10) R^(D241)L_(C1250) R^(D10) R^(D242) L_(C1251) R^(D10) R^(D243) L_(C1252) R^(D10)R^(D244) L_(C1253) R^(D10) R^(D245) L_(C1254) R^(D10) R^(D246) L_(C1255)R^(D55) R^(D193) L_(C1256) R^(D55) R^(D194) L_(C1257) R^(D55) R^(D195)L_(C1258) R^(D55) R^(D196) L_(C1259) R^(D55) R^(D197) L_(C1260) R^(D55)R^(D198) L_(C1261) R^(D55) R^(D199) L_(C1262) R^(D55) R^(D200) L_(C1263)R^(D55) R^(D201) L_(C1264) R^(D55) R^(D202) L_(C1265) R^(D55) R^(D203)L_(C1266) R^(D55) R^(D204) L_(C1267) R^(D55) R^(D205) L_(C1268) R^(D55)R^(D206) L_(C1269) R^(D55) R^(D207) L_(C1270) R^(D55) R^(D208) L_(C1271)R^(D55) R^(D209) L_(C1272) R^(D55) R^(D210) L_(C1273) R^(D55) R^(D211)L_(C1274) R^(D55) R^(D212) L_(C1275) R^(D55) R^(D213) L_(C1276) R^(D55)R^(D214) L_(C1277) R^(D55) R^(D215) L_(C1278) R^(D55) R^(D216) L_(C1279)R^(D55) R^(D217) L_(C1280) R^(D55) R^(D218) L_(C1281) R^(D55) R^(D219)L_(C1282) R^(D55) R^(D220) L_(C1283) R^(D55) R^(D221) L_(C1284) R^(D55)R^(D222) L_(C1285) R^(D55) R^(D223) L_(C1286) R^(D55) R^(D224) L_(C1287)R^(D55) R^(D225) L_(C1288) R^(D55) R^(D226) L_(C1289) R^(D55) R^(D227)L_(C1290) R^(D55) R^(D228) L_(C1291) R^(D55) R^(D229) L_(C1292) R^(D55)R^(D230) L_(C1293) R^(D55) R^(D231) L_(C1294) R^(D55) R^(D232) L_(C1295)R^(D55) R^(D233) L_(C1296) R^(D55) R^(D234) L_(C1297) R^(D55) R^(D235)L_(C1298) R^(D55) R^(D236) L_(C1299) R^(D55) R^(D237) L_(C1300) R^(D55)R^(D238) L_(C1301) R^(D55) R^(D239) L_(C1302) R^(D55) R^(D240) L_(C1303)R^(D55) R^(D241) L_(C1304) R^(D55) R^(D242) L_(C1305) R^(D55) R^(D243)L_(C1306) R^(D55) R^(D244) L_(C1307) R^(D55) R^(D245) L_(C1308) R^(D55)R^(D246) L_(C1309) R^(D37) R^(D193) L_(C1310) R^(D37) R^(D194) L_(C1311)R^(D37) R^(D195) L_(C1312) R^(D37) R^(D196) L_(C1313) R^(D37) R^(D197)L_(C1314) R^(D37) R^(D198) L_(C1315) R^(D37) R^(D199) L_(C1316) R^(D37)R^(D200) L_(C1317) R^(D37) R^(D201) L_(C1318) R^(D37) R^(D202) L_(C1319)R^(D37) R^(D203) L_(C1320) R^(D37) R^(D204) L_(C1321) R^(D37) R^(D205)L_(C1322) R^(D37) R^(D206) L_(C1323) R^(D37) R^(D207) L_(C1324) R^(D37)R^(D208) L_(C1325) R^(D37) R^(D209) L_(C1326) R^(D37) R^(D210) L_(C1327)R^(D37) R^(D211) L_(C1328) R^(D37) R^(D212) L_(C1329) R^(D37) R^(D213)L_(C1330) R^(D37) R^(D214) L_(C1331) R^(D37) R^(D215) L_(C1332) R^(D37)R^(D216) L_(C1333) R^(D37) R^(D217) L_(C1334) R^(D37) R^(D218) L_(C1335)R^(D37) R^(D219) L_(C1336) R^(D37) R^(D220) L_(C1337) R^(D37) R^(D221)L_(C1338) R^(D37) R^(D222) L_(C1339) R^(D37) R^(D223) L_(C1340) R^(D37)R^(D224) L_(C1341) R^(D37) R^(D225) L_(C1342) R^(D37) R^(D226) L_(C1343)R^(D37) R^(D227) L_(C1344) R^(D37) R^(D228) L_(C1345) R^(D37) R^(D229)L_(C1346) R^(D37) R^(D230) L_(C1347) R^(D37) R^(D231) L_(C1348) R^(D37)R^(D232) L_(C1349) R^(D37) R^(D233) L_(C1350) R^(D37) R^(D234) L_(C1351)R^(D37) R^(D235) L_(C1352) R^(D37) R^(D236) L_(C1353) R^(D37) R^(D237)L_(C1354) R^(D37) R^(D238) L_(C1355) R^(D37) R^(D239) L_(C1356) R^(D37)R^(D240) L_(C1357) R^(D37) R^(D241) L_(C1358) R^(D37) R^(D242) L_(C1359)R^(D37) R^(D243) L_(C1360) R^(D37) R^(D244) L_(C1361) R^(D37) R^(D245)L_(C1362) R^(D37) R^(D246) L_(C1363) R^(D143) R^(D193) L_(C1364)R^(D143) R^(D194) L_(C1365) R^(D143) R^(D195) L_(C1366) R^(D143)R^(D196) L_(C1367) R^(D143) R^(D197) L_(C1368) R^(D143) R^(D198)L_(C1369) R^(D143) R^(D199) L_(C1370) R^(D143) R^(D200) L_(C1371)R^(D143) R^(D201) L_(C1372) R^(D143) R^(D202) L_(C1373) R^(D143)R^(D203) L_(C1374) R^(D143) R^(D204) L_(C1375) R^(D143) R^(D205)L_(C1376) R^(D143) R^(D206) L_(C1377) R^(D143) R^(D207) L_(C1378)R^(D143) R^(D208) L_(C1379) R^(D143) R^(D209) L_(C1380) R^(D143)R^(D210) L_(C1381) R^(D143) R^(D211) L_(C1382) R^(D143) R^(D212)L_(C1383) R^(D143) R^(D213) L_(C1384) R^(D143) R^(D214) L_(C1385)R^(D143) R^(D215) L_(C1386) R^(D143) R^(D216) L_(C1387) R^(D143)R^(D217) L_(C1388) R^(D143) R^(D218) L_(C1389) R^(D143) R^(D219)L_(C1390) R^(D143) R^(D220) L_(C1391) R^(D143) R^(D221) L_(C1392)R^(D143) R^(D222) L_(C1393) R^(D143) R^(D223) L_(C1394) R^(D143)R^(D224) L_(C1395) R^(D143) R^(D225) L_(C1396) R^(D143) R^(D226)L_(C1397) R^(D143) R^(D227) L_(C1398) R^(D143) R^(D228) L_(C1399)R^(D143) R^(D229) L_(C1400) R^(D143) R^(D230) L_(C1401) R^(D143)R^(D231) L_(C1402) R^(D143) R^(D232) L_(C1403) R^(D143) R^(D233)L_(C1404) R^(D143) R^(D234) L_(C1405) R^(D143) R^(D235) L_(C1406)R^(D143) R^(D236) L_(C1407) R^(D143) R^(D237) L_(C1408) R^(D143)R^(D238) L_(C1409) R^(D143) R^(D239) L_(C1410) R^(D143) R^(D240)L_(C1411) R^(D143) R^(D241) L_(C1412) R^(D143) R^(D242) L_(C1413)R^(D143) R^(D243) L_(C1414) R^(D143) R^(D244) L_(C1415) R^(D143)R^(D245) L_(C1416) R^(D143) R^(D246)

wherein R^(D1) to R^(D246) have the following structures:


85. The compound of claim 82, wherein the compound has the Formula II:

wherein: M¹ is Pd or Pt; rings E and F are each independently a5-membered or 6-membered carbocyclic or heterocyclic ring; Z and Z′ areeach independently C or N; K¹ and K² are each independently selectedfrom the group consisting of a direct bond, O, and S, wherein at leastone of K¹ and K² is a direct bond; L¹ is an organic linker, L², L³ andL⁴ are each independently selected from the group consisting of a singlebond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′, wherein at leastone of L², L³ and L⁴ is present; X³ and X⁴ are each independently C orN; R^(E) and R^(F) each independently represent zero, mono, or up to amaximum allowed substitution to its associated ring; each of R′, R″,R^(E), and R^(F) is independently a hydrogen or a substituent selectedfrom the group consisting of deuterium, fluorine, alkyl, cycloalkyl,heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl,cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile,sulfanyl, and combinations thereof; and any two adjacent R^(A), R^(B),R, R′, R″ R^(E), and R^(F) can be joined or fused together to formaring.
 86. The compound of claim 85, wherein ring E and ring F are both6-membered aromatic rings; or ring F is a 5-membered or 6-memberedheteroaromatic ring.
 87. The compound of claim 85, wherein L¹ is O orCR′R″; and L² is a direct bond or NR′.
 88. The compound of claim 85,wherein the compound is selected from the group consisting of:

wherein: L^(1a) is selected from the group of —CR═N—, —CR′R″CR′R″—,—NR′BR—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—,—CR′═CR″CR₂—, —C(═CR—)—, and —C(═N—)—; L^(1b) is selected from the groupof —CR═N—, —CR₂—, —CR═CR′—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—,—CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR₂—, —C(═CR—)—, and—C(═N—)—; R^(Y) are each selected from the group consisting of alkyl,cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, andcombinations thereof; each R^(G) is independently a hydrogen or asubstituent selected from the group consisting of deuterium, fluorine,alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl,alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile,isonitrile, sulfanyl, and combinations thereof; and any two R^(A),R^(B), R^(E), R^(F), R^(G), R^(Y), R, R′ and R″ can be joined togetherto form a ring.
 89. An organic light emitting device (OLED) comprising:an anode; a cathode; and an organic layer disposed between the anode andthe cathode, wherein the organic layer comprises a compound comprising aligand L_(A) of Formula I:

wherein: each of Z¹, Z², Z³, Z⁴, Z⁵, and Z⁶ each independently C or N; Kis selected from the group consisting of a direct bond, O, and S; when Kis O or S, then Z⁶ is C; each of ring A1 and ring A2 is independently a5-membered or 6-membered carbocyclic or heterocyclic rings or amulticyclic fused-ring system comprising more than one 5-membered or6-membered carbocyclic or heterocyclic ring; each of R^(A) and R^(B) isindependently mono, up to a maximum allowed substitutions, or nosubstitution; the ligand L_(A) is coordinated to a metal M by the twoindicated dash lines; M is selected from the group consisting of Ru, Os,Ir, Pd, Pt, Cu, Ag, and Au; M is coordinated to at least one otherligand; L_(A) can be joined with other ligands to form a tridentate,tetradentate, pentadentate, or hexadentate ligand; L¹ is an organiclinker, when M is selected from the group consisting of Ru, Os, and Ir,then K is O or S; when M is selected from the group consisting of Pt,Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least onebond to oxygen or sulfur, and when M is selected from the groupconsisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then L¹ isselected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—,—CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR₂—,—C(═N—)—, and —C(═CR—)—; each R^(A), R^(B), R, R′, R″ is independently ahydrogen or a substituent selected from the group consisting ofdeuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and any two adjacent R^(A), R^(B), R, R′ and R″can be joined or fused together to form a ring.
 90. The OLED of claim89, wherein the organic layer further comprises a host, wherein hostcomprises at least one chemical moiety selected from the groupconsisting of triphenylene, carbazole, indolocarbazole,dibenzothiophene, dibenzofuran, dibenzoselenophene,5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene,aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene,aza-dibenzofuran, aza-dibenzoselenophene, andaza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
 91. The OLED ofclaim 90, wherein the host is selected from the group consisting of:

and combinations thereof.
 92. A consumer product comprising an organiclight-emitting device (OLED) comprising: an anode; a cathode; and anorganic layer disposed between the anode and the cathode, wherein theorganic layer comprises a compound comprising a ligand L_(A) of FormulaI:

wherein: each of Z¹, Z², Z³, Z⁴, Z⁵, and Z⁶ each independently C or N; Kis selected from the group consisting of a direct bond, O, and S; when Kis O or S, then Z⁶ is C; each of ring A1 and ring A2 is independently a5-membered or 6-membered carbocyclic or heterocyclic rings or amulticyclic fused-ring system comprising more than one 5-membered or6-membered carbocyclic or heterocyclic ring; each of R^(A) and R^(B) isindependently mono, up to a maximum allowed substitutions, or nosubstitution; the ligand L_(A) is coordinated to a metal M by the twoindicated dash lines; M is selected from the group consisting of Ru, Os,Ir, Pd, Pt, Cu, Ag, and Au; M is coordinated to at least one otherligand; L_(A) can be joined with other ligands to form a tridentate,tetradentate, pentadentate, or hexadentate ligand; L¹ is an organiclinker, when M is selected from the group consisting of Ru, Os, and Ir,then K is O or S; when M is selected from the group consisting of Pt,Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least onebond to oxygen or sulfur, and when M is selected from the groupconsisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then LI isselected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—,—CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR₂—,—C(═N—)—, and —C(═CR—)—; each R^(A), R^(B), R, R′, R″ is independently ahydrogen or a substituent selected from the group consisting ofdeuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and any two adjacent R^(A), R^(B), R, R′ and R″can be joined or fused together to form a ring.